Method for producing photosensitive composition, and method for producing premix liquid, photosensitive composition, dry film, and resist film

Abstract

Provided is a production method for a chemically amplified photosensitive composition capable of reducing foreign matter derived from a sulfur-containing compound. The production method for a chemically amplified photosensitive composition containing an acid generator (A) that generates an acid by irradiation of active light or a radiation, a sulfur-containing compound (C) that is solid at room temperature, a solvent (S1) having a polar term δp of a Hansen solubility parameter of 10 (MPa 0.5 ) or more, and a solvent (S2) that is different from the solvent (S1), includes a step of dissolving the sulfur-containing compound (C) in the solvent (S1) to prepare a sulfur-containing compound (C) solution, and a step of mixing the sulfur-containing compound (C) solution, the acid generator (A), and the solvent (S2).

Description

Technical Field

[0001] This invention relates to a method for manufacturing a chemically amplified photosensitive composition, a premixed liquid for preparing a chemically amplified photosensitive composition that can be used in the method for manufacturing the chemically amplified photosensitive composition, a chemically amplified photosensitive composition that can be manufactured by the above-described method for manufacturing a chemically amplified photosensitive composition, a method for manufacturing a photosensitive dry film having a photosensitive layer composed of the above-described chemically amplified photosensitive composition, and a method for manufacturing a patterned resist film using the above-described chemically amplified photosensitive composition. Background Technology

[0002] Currently, photofabrication has become the mainstream of precision micro-machining technology. Photofabrication refers to the general term for technologies that involve coating a photoresist composition onto the surface of a workpiece to form a photoresist layer, using photolithography to pattern the photoresist layer, and then using the patterned photoresist layer (photoresist pattern) as a mask for chemical etching, electrolytic etching, or electroforming (primarily electroplating), to manufacture various precision components such as semiconductor packages.

[0003] Furthermore, in recent years, with the miniaturization of electronic devices, high-density mounting technology for semiconductor packaging has been continuously advancing, seeking to increase the mounting density based on multi-pin thin-film mounting, miniaturization of package size, 2D mounting technology using flip chips, and 3D mounting technology. In such high-density mounting technologies, protruding electrodes (mounting terminals) such as bumps on the package, or metal pillars connecting rewiring extending from peripheral terminals on the wafer to the mounting terminals, are precisely positioned on the substrate as connection terminals.

[0004] In the photoelectric processing described above, photoresist compositions are used. Among such photoresist compositions, chemically amplified photosensitive compositions containing an acid-generating agent are known (see Patent Documents 1, 2, etc.). Chemically amplified photosensitive compositions refer to compositions in which acid is generated from the acid-generating agent by irradiation (exposure), and the diffusion of the acid is promoted by heat treatment, thereby causing an acid-catalyzed reaction relative to the matrix resin or the like in the composition, thus changing its alkali solubility.

[0005] Such chemically amplified photosensitive compositions are used not only for the formation of patterned insulating films and etching masks, but also for forming plated shapes such as bumps, metal pillars, and Cu redistribution wiring through plating processes. Specifically, using a chemically amplified photosensitive composition, a photoresist layer of desired thickness is formed on a support such as a metal substrate. This layer is then exposed and developed using a predetermined mask pattern to form a photoresist pattern used as a mold to selectively remove (strip) the portion from which the plated shape is formed. Then, a conductor such as copper is embedded into the removed portion (non-resist portion) through plating, and the surrounding photoresist pattern is removed, thereby forming bumps, metal pillars, and Cu redistribution wiring.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 9-176112

[0009] Patent Document 2: Japanese Patent Application Publication No. 11-52562

[0010] Patent Document 3: Japanese Patent Application Publication No. 2015-87759

[0011] Patent Document 4: Japanese Patent Application Publication No. 2016-502142

[0012] Patent Document 5: Japanese Patent Application Publication No. 2019-514072 Summary of the Invention

[0013] The technical problem that the invention aims to solve

[0014] Generally speaking, when forming a resist pattern, it is generally desirable for its cross-sectional shape to be rectangular. Especially in the formation of connecting terminals such as bumps or metal pillars using the above-mentioned plating process, or in the formation of Cu rewiring, it is highly desirable for the non-resist portion of the resist pattern that becomes a mold to have a rectangular cross-sectional shape.

[0015] In the process of forming the plated shape, by making the cross-sectional shape of the non-resistant portion of the resist pattern that becomes the mold rectangular, the contact area between the bottom surface of the connecting terminals such as bumps and metal pillars, and the Cu redistribution wiring, and the support body can be sufficiently ensured. This facilitates the formation of connecting terminals or Cu redistribution wiring that have good adhesion to the support body.

[0016] Techniques for mixing sulfur-containing compounds to improve the shape of resist patterns have been disclosed (Patent Documents 3-5).

[0017] However, when forming a resist pattern using a chemically amplified resist composition containing a sulfur-containing compound, as disclosed in Patent Documents 3-5, foreign matter often appears in the chemically amplified resist composition or in the resulting resist pattern. This foreign matter originates from the sulfur-containing compound contained in the chemically amplified resist composition.

[0018] If foreign matter is present in the resist pattern, it will be difficult to form the desired shape of the coated or etched object when the resist pattern is used as a mold or etching mask for forming the coated object.

[0019] In addition, the chemically amplified resist composition is often used by filtration. However, when foreign matter from sulfur-containing compounds is removed by filtration, the desired effect of improving the shape of the resist pattern may be compromised due to the reduced content of sulfur-containing compounds in the chemically amplified resist composition.

[0020] Therefore, there is a desire for a method for manufacturing a chemically amplified resist composition that can reduce the amount of foreign matter originating from sulfur-containing compounds, and a chemically amplified resist composition manufactured by the method.

[0021] The present invention was made in view of the above-mentioned technical problems, and its object is to provide a method for manufacturing a chemically amplified photosensitive composition that can reduce the amount of foreign matter from sulfur-containing compounds, a premixed liquid for preparing the chemically amplified photosensitive composition that can be used in the method for manufacturing the chemically amplified photosensitive composition, a chemically amplified photosensitive composition that can be manufactured by the above-described method for manufacturing the chemically amplified photosensitive composition, a method for manufacturing a photosensitive dry film having a photosensitive layer composed of the above-described chemically amplified photosensitive composition, and a method for manufacturing a patterned resist film using the above-described chemically amplified photosensitive composition.

[0022] Solution to the above technical problems

[0023] The inventors have continuously and diligently researched in order to achieve the above-mentioned objectives, and have discovered that in manufacturing a chemically amplified photosensitive composition comprising an acid-generating agent (A) that generates acid upon irradiation with active light or radiation and a sulfur-containing compound (C) that is solid at room temperature, the sulfur-containing compound (C) is pre-dissolved in a solution with a polarity term δp of the Hansen solubility parameter of 10 MPa. 0.5 After preparing a sulfur-containing compound (C) solution using the solvent (S1) above, the sulfur-containing compound (C) solution, the acid-generating agent (A), and a solvent (S2) different from the solvent (S1) are mixed to solve the above-mentioned technical problems, thereby completing the present invention. Specifically, the present invention provides the following solution.

[0024] The first aspect of the present invention is a method for manufacturing a chemically amplified photosensitive composition, wherein the chemically amplified photosensitive composition contains an acid-generating agent (A) that generates acid upon irradiation by active light or radiation, a sulfur-containing compound (C) that is solid at room temperature, and a polarity term δp of the Hansen solubility parameter of 10 MPa. 0.5 The method for manufacturing the chemically amplified photosensitive composition includes: a solvent (S1) and a solvent (S2) different from solvent (S1).

[0025] The process of preparing a solution of sulfur-containing compound (C) by dissolving a sulfur-containing compound (C) in a solvent (S1); and

[0026] The process of mixing a sulfur-containing compound (C) solution, an acid-generating agent (A), and a solvent (S2).

[0027] The second aspect of the present invention is a premixed solution for preparing a chemically magnified photosensitive composition, containing a sulfur-containing compound (C) that is solid at room temperature, and a polarity term δp of the Hansen solubility parameter of 10 MPa. 0.5 The above solvent (S1) contains sulfur-containing compounds (C) which are dissolved in the solvent (S1).

[0028] The third aspect of the present invention is a chemically magnified photosensitive composition containing an acid-generating agent (A) that produces acid upon irradiation by active light or radiation, a sulfur-containing compound (C) that is solid at room temperature, and a polarity term δp of the Hansen solubility parameter of 10 MPa. 0.5 Solvents above (S1) and solvents different from solvent (S1) (S2)

[0029] The content of solvent (S1) relative to the total mass of solvent (S1) and solvent (S2) is greater than 0% by mass and less than 5% by mass.

[0030] The fourth aspect of the present invention is a method for manufacturing a photosensitive dry film, comprising coating a substrate film with the chemically amplified photosensitive composition of the third aspect to form a photosensitive layer.

[0031] The fifth aspect of the present invention is a method for manufacturing a patterned resist film, comprising:

[0032] In the lamination process, a photosensitive layer composed of the chemically amplified photosensitive composition of the third scheme is laminated on the substrate.

[0033] The exposure process involves selectively irradiating the photosensitive layer with active light or radiation.

[0034] The developing process involves developing the exposed photosensitive layer.

[0035] Invention Effects

[0036] According to the present invention, a method for manufacturing a chemically amplified photosensitive composition capable of reducing the amount of foreign matter originating from sulfur-containing compounds can be provided; a premixed liquid for preparing a chemically amplified photosensitive composition that can be used in the method for manufacturing the chemically amplified photosensitive composition; a chemically amplified photosensitive composition that can be manufactured by the method for manufacturing the chemically amplified photosensitive composition; a method for manufacturing a photosensitive dry film having a photosensitive layer composed of the chemically amplified photosensitive composition; and a method for manufacturing a patterned resist film using the above-described chemically amplified photosensitive composition. Detailed Implementation

[0037] Method for manufacturing chemically amplified photosensitive compositions, chemically amplified photosensitive compositions, and premixed solutions for preparing chemically amplified photosensitive compositions.

[0038] Using the method for manufacturing the chemically amplified photosensitive composition described later, it is possible to manufacture an acid-generating agent (A) (hereinafter also referred to as acid-generating agent (A)) that generates acid upon irradiation by active light or radiation, a sulfur-containing compound (C) that is solid at room temperature, and a Hansen solubility parameter with a polarity term δp of 10 MPa. 0.5 The photosensitive composition is a chemically amplified composition using a solvent (S1) and a solvent (S2) different from the solvent (S1). The method for manufacturing the photosensitive composition described later includes: a step of preparing a sulfur-containing compound (C) solution by dissolving a sulfur-containing compound (C) in a solvent (S1); and a step of mixing the sulfur-containing compound (C) solution, an acid-generating agent (A), and a solvent (S2).

[0039] First, a chemically amplified photosensitive composition manufactured by a method for manufacturing a chemically amplified photosensitive composition will be described.

[0040] As a chemically amplified photosensitive composition, it contains an acid-producing agent (A), a sulfur-containing compound (C) that is solid at room temperature, and a polarity term δp of the Hansen solubility parameter of 10 MPa. 0.5 The solvent (S1) above and the solvent (S2) different from the solvent (S1) are the same as those in conventionally known chemically amplified photosensitive compositions containing an acid-generating agent (A).

[0041] As a chemically amplified photosensitive composition, it can be a positive photosensitive composition that increases the solubility in the developer by utilizing the acid generated through exposure, or a negative photosensitive composition that decreases the solubility in the developer by utilizing the acid generated through exposure.

[0042] Examples of positively amplified chemically photosensitive compositions include photosensitive compositions containing an acid-producing agent (A), a sulfur-containing compound (C), a solvent (S1), and a solvent (S2), as well as a resin (B) whose solubility in alkali is increased due to the action of an acid. The resin (B) has alkali-soluble groups protected by groups deprotected by the action of an acid, such as tert-butyl, tert-butoxycarbonyl, tetrahydropyranyl, acetal, and trimethylsilyl.

[0043] Examples of negatively typed, chemically amplified photosensitive compositions include photosensitive compositions that contain an acid-generating agent (A), a sulfur-containing compound (C), a solvent (S1), and a solvent (S2), as well as a condensing agent such as hydroxymethyl melamine and a resin such as phenolic varnish resin that can be crosslinked by the condensing agent. When the above-mentioned photosensitive composition is exposed, it cures due to a crosslinking reaction caused by the acid generated during exposure.

[0044] Furthermore, as a negatively amplified photosensitive composition, it is preferable to include an epoxy compound along with an acid-generating agent (A), a sulfur-containing compound (C), a solvent (S1), and a solvent (S2). When the above-mentioned photosensitive composition is exposed, the cationic polymerization of the epoxy compound caused by the acid generated during exposure is promoted, resulting in the curing of the photosensitive composition.

[0045] Among these chemically amplified photosensitive compositions, from the perspective that it is particularly easy to achieve the desired level of high sensitivity, or from the perspective that it is easy to impart the desired properties to the patterned resist film by adjusting the type or ratio of structural units of the resin (B) whose solubility in alkali is increased by the action of acid, a chemically amplified positive photosensitive composition comprising an acid-generating agent (A), a resin (B) whose solubility in alkali is increased by the action of acid, and an acid diffusion inhibitor (F) is preferred.

[0046] Hereinafter, as a representative example of a photosensitive composition, the necessary or optional components and manufacturing method of a chemically amplified positive photosensitive composition (hereinafter also referred to as a photosensitive composition) containing an acid-generating agent (A), a resin (B) whose solubility in alkali increases due to the action of acid (hereinafter also referred to as resin (B)), a sulfur-containing compound (C), a solvent (S1), and a solvent (S2) will be described.

[0047] In addition, the acid-generating agent (A), sulfur-containing compound (C), solvent (S1), and solvent (S2) described below can also be used in photosensitive compositions other than the positive photosensitive compositions described later.

[0048] <Acid-producing agent (A)>

[0049] The acid-generating agent (A) is a compound that produces acid through irradiation with active light or radiation. There is no particular limitation as long as the compound produces acid directly or indirectly through light. Preferably, the acid-generating agents of the first to fifth embodiments described below are preferred as acid-generating agents (A). Hereinafter, preferred embodiments of the acid-generating agent (A) preferably used in the positive photosensitive composition will be described as the first to fifth embodiments.

[0050] As a first option among acid-producing agents (A), a compound represented by the following formula (a1) can be cited.

[0051] [Chemistry 1]

[0052]

[0053] In the above formula (a1), X 1a The valence g represents a sulfur or iodine atom, where g is 1 or 2. h indicates the number of repeating units in the structure within the brackets. R 1a To be with X 1a The bonded organic group represents an aryl group with 6 to 30 carbon atoms, a heterocyclic group with 4 to 30 carbon atoms, an alkyl group with 1 to 30 carbon atoms, an alkenyl group with 2 to 30 carbon atoms, or an alkynyl group with 2 to 30 carbon atoms. R 1a It can be substituted by at least one group selected from alkyl, hydroxy, alkoxy, alkyl carbonyl, aryl carbonyl, alkoxy carbonyl, aryloxy carbonyl, arylthio carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkyl sulfinyl, aryl sulfinyl, alkyl sulfonyl, aryl sulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. 1a The number of elements is g + h(g-1) + 1, R 1a They can be the same as each other or different. Furthermore, two or more R's... 1a They can bond directly to each other or via -O-, -S-, -SO-, -SO2-, -NH-, -NR 2a -, -CO-, -COO-, -CONH-, and alkylene or phenylene groups with 1 to 3 carbon atoms are bonded together to form a group containing X. 1a The ring structure. R 2a It is an alkyl group with 1 to 5 carbon atoms or an aryl group with 6 to 10 carbon atoms.

[0054] X 2a The structure is represented by the following formula (a2).

[0055] [Chemistry 2]

[0056]

[0057] In the above formula (a2), X 4a X represents a divalent group in alkylene compounds with 1 to 8 carbon atoms, arylene compounds with 6 to 20 carbon atoms, or heterocyclic compounds with 8 to 20 carbon atoms. 4a It can be substituted by at least one group selected from the group consisting of alkyl groups having 1 to 8 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, aryl, hydroxyl, cyano, and nitro groups having 6 to 10 carbon atoms, and halogens. 5a This represents -O-, -S-, -SO-, -SO2-, -NH-, -NR 2a -, -CO-, -COO-, -CONH-, and alkylene or phenylene compounds with 1 to 3 carbon atoms. h indicates the number of repeating units in the parentheses. h+1 X 4a And h X 5a They can be the same or different. R 2a Same as the definition above.

[0058] X 3a - As counterions to onyx, examples include fluoroalkyl fluorophosphate anions represented by formula (a17) or borate anions represented by formula (a18).

[0059] [Chemistry 3]

[0060] [(R 3a ) j PF 6-j (a17)

[0061] In the above formula (a17), R 3a This indicates an alkyl group obtained by replacing more than 80% of its hydrogen atoms with fluorine atoms. j represents the number of alkyl groups, an integer between 1 and 5. j alkyl groups 3a They can be the same or different.

[0062] [Chemistry 4]

[0063]

[0064] In the above formula (a18), R 4a ~R 7a Each of the above independently represents a fluorine atom or a phenyl group, wherein some or all of the hydrogen atoms of the phenyl group may be substituted with at least one of the groups consisting of a fluorine atom and a trifluoromethyl group.

[0065] Examples of onium ions in compounds represented by formula (a1) above include triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonyl)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonyl}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonyl]phenyl}sulfide, and 4-(4-benzoyl-2-chlorobenzene) 7-Isopropyl-9-oxo-10-thio-9,10-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-Isopropyl-9-oxo-10-thio-9,10-dihydroanthracene-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonyl]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4-(4- Benzoylphenylthio)phenyl diphenylsulfonium, diphenylbenzoylmethylsulfonium, 4-hydroxyphenylmethylbenzylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, 4-hydroxyphenylmethylbenzoylmethylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl]diphenylsulfonium, Octadecylmethylbenzoylmethylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl)iodonium, bis(4-methoxyphenyl)iodonium, (4-octoxyphenyl)phenyliodonium, bis(4-decoxyphenyl)phenyliodonium, 4-(2-hydroxytetradecoxy)phenylphenyliodonium, 4-isopropylphenyl(p-tolyl)iodonium, or 4-isobutylphenyl(p-tolyl)iodonium, etc.

[0066] Among the onnnium ions in the compounds represented by the above formula (a1), the preferred onnnium ion is the sulfonium ion represented by the following formula (a19).

[0067] [Chemistry 5]

[0068]

[0069] In the above formula (a19), R 8a Each of these groups independently represents a group selected from the group consisting of hydrogen atom, alkyl, hydroxyl, alkoxy, alkyl carbonyl, alkyl carbonyloxy, alkyloxy carbonyl, halogen atom, aryl group which may have substituents, and aryl carbonyl. 2a This indicates that X in the above formula (a1) is related to... 2a Same meaning.

[0070] Specific examples of sulfonium ions represented by the above formula (a19) include 4-(phenylthio)phenyl diphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenyl bis(4-fluorophenyl)sulfonium, 4-(4-benzoylphenylthio)phenyl diphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetylphenylthio)phenyl]diphenylsulfonium, and diphenyl[4-(p-triphenylthio)phenyl]diphenylsulfonium.

[0071] In the fluoroalkyl fluorophosphate anion represented by the above formula (a17), R 3a The alkyl group obtained by substitution with fluorine atoms preferably has 1 to 8 carbon atoms, and more preferably 1 to 4 carbon atoms. Specific examples of alkyl groups include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and octyl; branched-chain alkyl groups such as isopropyl, isobutyl, sec-butyl, and tert-butyl; and cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The proportion of hydrogen atoms in the alkyl group that are substituted by fluorine atoms is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkyl fluorophosphate represented by the above formula (a1) decreases.

[0072] Specially selected R 3a It is a straight-chain or branched perfluoroalkyl group with 1 to 4 carbon atoms and a fluorine substitution rate of 100%. Specific examples include CF3, CF3CF2, (CF3)2CF, CF3CF2CF2, CF3CF2CF2CF2, (CF3)2CFCF2, CF3CF2(CF3)CF, and (CF3)3C. 3a The number j is an integer between 1 and 5, preferably between 2 and 4, and especially preferably 2 or 3.

[0073] As a preferred example of a fluoroalkyl fluorophosphate anion, [(CF3CF2)2PF4] can be cited. - [(CF3CF2)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CF)3PF3] - [(CF3CF2CF2)2PF4] - [(CF3CF2CF2)3PF3] - [((CF3)2CFCF2)2PF4] - [((CF3)2CFCF2)3PF3] - [(CF3CF2CF2CF2)2PF4] -Or [(CF3CF2CF2)3PF3] - Of which, [(CF3CF2)3PF3] is particularly preferred. - [(CF3CF2CF2)3PF3] - [((CF3)2CF)3PF3] - [((CF3)2CF)2PF4] - [((CF3)2CFCF2)3PF3] - Or [((CF3)2CFCF2)2PF4] - .

[0074] As a preferred specific example of the borate anion represented by the above formula (a18), tetratetra(pentafluorophenyl)borate ([B(C6F5)4]) can be cited. - ), tetra[(trifluoromethyl)phenyl]borate ([B(C6H4CF3)4] - ), difluorobis(pentafluorophenyl)borate ([(C6F5)2BF2] - ), trifluoro(pentafluorophenyl)borate ([(C6F5)BF3] - ), tetra(difluorophenyl)borate ([B(C6H3F2)4] - ), etc. Of particular preference is tetra(pentafluorophenyl)borate ([B(C6F5)4]). - ).

[0075] As a second option in acid-producing agent (A), examples include 2,4-bis(trichloromethyl)-6-piperyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(5-ethyl-2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-furanyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(2-(2-(2-furanyl)vinyl) ... 2,4-bis(trichloromethyl)-6-[2-(3,5-diethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy-5-propoxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)vinyl]triazine, 2,4-bis(trichloromethyl)-6-(3,4-methylenedioxyphenyl)triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4- 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyltriazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyltriazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyltriazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furanyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furanyl)vinyl]- Halogenated triazine compounds such as 4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,5-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1,3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine, and trihalomethanes, and halogenated triazine compounds represented by the following formula (a3), such as tris(2,3-dibromopropyl)isocyanurate.

[0076] [Chemistry 6]

[0077]

[0078] In the above formula (a3), R 9a R 10a R 11a Each can be represented independently as a haloalkyl group.

[0079] Furthermore, as a third option among the acid-producing agents (A), examples include α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzenesulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and compounds containing an oxime sulfonate group represented by the following formula (a4).

[0080] [Chemistry 7]

[0081]

[0082] In the above formula (a4), R 12a R represents an organic group that is monovalent, divalent, or trivalent. 13a This indicates a substituted or unsubstituted saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group, and n indicates the number of repeating units in the structure within the parentheses.

[0083] In formula (a4) above, aromatic groups can be exemplified by aryl groups such as phenyl and naphthyl, or heteroaryl groups such as furanyl and thiophene. They may have one or more suitable substituents on the ring, such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. Additionally, R... 13a Alkyl groups having 1 to 6 carbon atoms are particularly preferred; examples include methyl, ethyl, propyl, and butyl. R is particularly preferred. 12a Aromatic groups, R 13a Compounds consisting of alkyl groups having 1 to 4 carbon atoms.

[0084] As an acid-producing agent represented by the above formula (a4), R can be cited as an example when n=1. 12a It is any one of phenyl, methylphenyl, and methoxyphenyl, and R 13a Compounds containing methyl groups, specifically, include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl)acetonitrile, and [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophene-3-ethylene](o-tolyl)acetonitrile. When n = 2, as acid-producing agents represented by the above formula (a4), examples include acid-producing agents represented by the following formula.

[0085] [Chemistry 8]

[0086]

[0087] Furthermore, as a fourth option in the acid-producing agent (A), an onium salt having a naphthalene ring in the cation portion can be cited as an example. "Having a naphthalene ring" means having a structure derived from naphthalene, specifically a structure having at least two rings, and maintaining their aromaticity. This naphthalene ring can have substituents such as straight-chain or branched alkyl groups, hydroxyl groups, or straight-chain or branched alkoxy groups having 1 to 6 carbon atoms. Although the structure derived from the naphthalene ring can be a monovalent group (free valence of 1) or a divalent group (free valence of 2 or more), it is desirable to be a monovalent group (wherein, the portion bonded to the aforementioned substituents is removed to count the free valence). The number of naphthalene rings is preferably 1 to 3 or less.

[0088] As such a cation portion of an onium salt having a naphthalene ring in the cation portion, the structure represented by the following formula (a5) is preferred.

[0089] [Chemistry 9]

[0090]

[0091] In the above formula (a5), R 14a R 15a R 16a At least one of them represents a group represented by formula (a6) below, and the remainder represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a phenyl group that may have substituents, a hydroxyl group, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, R 14a R 15a R 16a One of them is a group represented by the following formula (a6), and the other two are independently linear or branched alkylene groups with 1 to 6 carbon atoms, and their ends can be bonded together to form a ring.

[0092] [Chemistry 10]

[0093]

[0094] In the above formula (a6), R 17a R 18a Each of the following can be independently represented as a hydroxyl group, a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, or a straight-chain or branched alkyl group having 1 to 6 carbon atoms. 19aThis indicates a straight-chain or branched alkylene group with a single bond or having 1 to 6 carbon atoms that may have substituents. l and m each independently represent an integer from 0 to 2, and l+m is 3 or less. Where multiple R groups are present... 17a In the case of R, they can be the same as each other or different. Furthermore, when there are multiple R... 18a In this case, they can be the same as each other or different.

[0095] From the perspective of compound stability, the above R 14a R 15a R 16a The number of groups represented by the above formula (a6) is preferably one, and the remainder are straight-chain or branched alkylene groups with 1 to 6 carbon atoms, whose ends can be bonded to form a ring. In this case, the above two alkylene groups contain sulfur atoms to form a three- to nine-membered ring. The number of atoms constituting the ring (including sulfur atoms) is preferably 5 to 6.

[0096] Furthermore, examples of substituents that the aforementioned alkylene group may have include oxygen atoms (in which case, together with the carbon atoms constituting the alkylene group, they form a carbonyl group), hydroxyl groups, etc.

[0097] Furthermore, examples of substituents that phenyl groups may have include hydroxyl groups, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, and straight-chain or branched alkyl groups having 1 to 6 carbon atoms.

[0098] Preferred structures for these cation portions include those represented by formulas (a7) and (a8), with the structure represented by formula (a8) being particularly preferred.

[0099] [Chemistry 11]

[0100]

[0101] The cation could be either an iodonium salt or a matte salt, but from the perspective of acid production efficiency, a matte salt would be preferred.

[0102] Therefore, the preferred anion for the anion portion of an onium salt having a naphthalene ring in the cation portion is preferably an anion that can form a sulfonium salt.

[0103] The anionic portion of such an acid-producing agent is a fluoroalkyl sulfonate ion or an aryl sulfonate ion in which some or all of the hydrogen atoms are fluorinated.

[0104] The alkyl group in the fluoroalkyl sulfonate ion can be a straight-chain, branched, or cyclic alkyl group with 1 to 20 carbon atoms. From the perspective of the size of the generated acid and its diffusion distance, a carbon number of 1 to 10 is preferred. In particular, branched or cyclic alkyl groups are preferred because they have shorter diffusion distances. Furthermore, from the viewpoint of being able to synthesize it inexpensively, methyl, ethyl, propyl, butyl, octyl, and the like are preferred groups.

[0105] The aryl group in the aryl sulfonate ion is an aryl group with 6 to 20 carbon atoms, and examples include phenyl and naphthyl groups that can be substituted or not substituted by alkyl or halogen atoms. In particular, from the viewpoint of being able to synthesize it inexpensively, aryl groups with 6 to 10 carbon atoms are preferred. Specific examples of preferred aryl groups include phenyl, toluenesulfonyl, ethylphenyl, naphthyl, methylnaphthyl, etc.

[0106] In the aforementioned fluoroalkyl sulfonate ions or aryl sulfonate ions, the fluorination rate is preferably 10% to 100% when some or all of the hydrogen atoms are fluorinated, more preferably 50% to 100%, and particularly preferred is the substance obtained by replacing all hydrogen atoms with fluorine atoms because the acid strength increases. Examples of such substances include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctanesulfonate, and perfluorobenzenesulfonate.

[0107] Among them, the preferred anion section can be represented by the following formula (a9).

[0108] [Chemistry 12]

[0109]

[0110] In the above equation (a9), R 20a These are groups represented by the following formulas (a10), (a11), and (a12).

[0111] [Chemistry 13]

[0112]

[0113] In equation (a10) above, x represents an integer greater than 1 and less than 4. Furthermore, in equation (a11) above, R... 21a The group represents a hydrogen atom, a hydroxyl group, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, or a straight-chain or branched alkoxy group having 1 to 6 carbon atoms, where y represents an integer of 1 to 3. From a safety perspective, trifluoromethanesulfonate or perfluorobutanesulfonate are preferred.

[0114] In addition, as an anion section, a nitrogen-containing anion section represented by the following formulas (a13) and (a14) can also be used.

[0115] [Chemistry 14]

[0116]

[0117] In the above equations (a13) and (a14), X a This refers to a straight-chain or branched alkylene group obtained by replacing at least one hydrogen atom with a fluorine atom, wherein the alkylene group has 2 to 6 carbon atoms, preferably 3 to 5, and most preferably 3 carbon atoms. Furthermore, Y a Z a Each of the above refers independently to a straight-chain or branched alkyl group obtained by replacing at least one hydrogen atom with a fluorine atom, wherein the alkyl group has 1 to 10 carbon atoms, preferably 1 to 7, and more preferably 1 to 3.

[0118] X a The number of carbon atoms in the alkylene group or Y a Z a The smaller the number of carbon atoms in the alkyl group, the better its solubility in organic solvents, and therefore it is preferred.

[0119] Furthermore, in X a alkylene or Y a Z a In an alkyl group, the more hydrogen atoms replaced by fluorine atoms, the stronger the acid, which is therefore preferred. The proportion of fluorine atoms in the alkylene or alkyl group, i.e., the fluorination rate, is preferably 70% to 100%, more preferably 90% to 100%, and most preferably a perfluoroalkylene or perfluoroalkyl group obtained by replacing all hydrogen atoms with fluorine atoms.

[0120] Compounds that are preferred as onium salts having a naphthalene ring in the cation portion include those represented by the following formulas (a15) and (a16).

[0121] [Chemistry 15]

[0122]

[0123] Furthermore, as a fifth option in acid-producing agent (A), examples include bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4-dimethylphenylsulfonyl)diazomethane, and other bissulfonyl diazonium methane derivatives; nitrobenzyl derivatives such as 2-nitrobenzyl p-toluenesulfonic acid, 2,6-dinitrobenzyl p-toluenesulfonic acid, nitrobenzyl toluenesulfonic acid, dinitrobenzyl toluenesulfonic acid, nitrobenzyl sulfonate, nitrobenzyl carbonate, and dinitrobenzyl carbonate; and pyrogallol trimethylsulfonate, pyrogallol tritoluenesulfonate, toluenesulfonyl benzyl ester, benzyl sulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyloxymaleimide, and N-methylsulfonyl... Sulfonates such as oxy-phthalimide; trifluoromethanesulfonates such as N-(trifluoromethanesulfonyloxy)phthalimide, N-(trifluoromethanesulfonyloxy)-1,8-naphthalenediamide, and N-(trifluoromethanesulfonyloxy)-4-butyl-1,8-naphthalenediamide; ononium salts such as diphenyliodonium hexafluorophosphate, (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, and (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin toluene sulfonate and α-methylbenzoin toluene sulfonate; and other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazoonium salts, and benzyl carbonate.

[0124] The acid-generating agent (A) can be used alone or in combination with two or more other agents. Furthermore, the content of the acid-generating agent (A) relative to the total solid content of the positive photosensitive composition is preferably 0.1% by mass to 10% by mass, more preferably 0.2% by mass to 6% by mass, and particularly preferably 0.5% by mass to 3% by mass. By keeping the amount of acid-generating agent (A) within the above range, it is easy to prepare a positive photosensitive composition with good sensitivity, a homogeneous solution, and excellent storage stability.

[0125] <Resin (B)>

[0126] The resin (B) whose solubility in alkali increases due to the action of acid is not particularly limited, and any resin whose solubility in alkali increases due to the action of acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of phenolic varnish resin (B1), polyhydroxystyrene resin (B2), and acrylic resin (B3).

[0127] [Phenolic varnish resin (B1)]

[0128] As a phenolic varnish resin (B1), a resin comprising structural units represented by the following formula (b1) can be used.

[0129] [Chemistry 16]

[0130]

[0131] In the above formula (b1), R 1b R represents an acid dissociation and solubility inhibition group. 2b R 3b Each can be used independently to represent an alkyl group having 1 to 6 hydrogen atoms or carbon atoms.

[0132] As for the above R 1b The acid dissociation and dissolution inhibition group represented is preferably a group represented by the following formulas (b2) and (b3), a straight-chain, branched, or cyclic alkyl group, vinyloxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, or trialkylsilyl group having 1 to 6 carbon atoms.

[0133] [Chemistry 17]

[0134]

[0135] In equations (b2) and (b3) above, R 4b R 5b Each of the following independently represents a hydrogen atom or a straight-chain or branched alkyl group having 1 to 6 carbon atoms: R 6b R represents a straight-chain, branched, or cyclic alkyl group having 1 to 10 carbon atoms. 7b It indicates a straight-chain, branched, or cyclic alkyl group with 1 to 6 carbon atoms, and o indicates 0 or 1.

[0136] Examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Examples of cyclic alkyl groups include cyclopentyl and cyclohexyl.

[0137] Here, examples of acid dissociation-inhibiting groups represented by formula (b2) above include methoxyethyl, ethoxyethyl, n-propoxyethyl, isopropoxyethyl, n-butoxyethyl, isobutoxyethyl, tert-butoxyethyl, cyclohexyloxyethyl, methoxypropyl, ethoxypropyl, 1-methoxy-1-methyl-ethyl, and 1-ethoxy-1-methylethyl. Furthermore, examples of acid dissociation-inhibiting groups represented by formula (b3) above include tert-butoxycarbonyl and tert-butoxycarbonylmethyl. Additionally, examples of trialkylsilyl groups include trimethylsilyl, tri-tert-butyldimethylsilyl, and groups where each alkyl group has 1 to 6 carbon atoms.

[0138] [Polyhydroxystyrene resin (B2)]

[0139] As a polyhydroxystyrene resin (B2), a resin comprising structural units represented by the following formula (b4) can be used.

[0140] [Chemistry 18]

[0141]

[0142] In equation (b4) above, R 8b R indicates an alkyl group having 1 to 6 hydrogen atoms or carbon atoms. 9b This indicates an acid dissociation and dissolution inhibition group.

[0143] The aforementioned alkyl groups having 1 to 6 carbon atoms are, for example, straight-chain, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. Examples of straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl, while examples of cyclic alkyl groups include cyclopentyl and cyclohexyl.

[0144] As mentioned above, R 9b The acid dissociation dissolution inhibition group indicated can be the same acid dissociation dissolution inhibition group as those exemplified in formulas (b2) and (b3) above.

[0145] Furthermore, for the purpose of appropriately controlling physical and chemical properties, polyhydroxystyrene resin (B2) can contain other polymerizable compounds as structural units. Examples of such polymerizable compounds include known free radical polymerizable compounds and anionic polymerizable compounds. Other examples include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives with carboxyl and ester bonds such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and hydroxyalkyl methacrylates such as 2-hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Classes include: phenyl methacrylate, benzyl methacrylate, and other aryl methacrylates; diethyl maleate, dibutyl fumarate, and other dicarboxylic acid diesters; vinyl-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl acetate and other vinyl-containing aliphatic compounds; butadiene, isoprene, and other conjugated dienes; acrylonitrile, methacrylonitrile, and other nitrile-containing polymeric compounds; vinyl chloride, vinylidene chloride, and other chlorine-containing polymeric compounds; and acrylamide, methacrylamide, and other polymeric compounds containing amide bonds.

[0146] [Acrylic resin (B3)]

[0147] As for acrylic resin (B3), there are no particular limitations as long as it is an acrylic resin whose solubility in alkali increases due to the action of acid, and which has been mixed in various photosensitive compositions.

[0148] The acrylic resin (B3) preferably contains structural units (b-3) derived from acrylates containing, for example, -SO2- cyclic groups or lactone cyclic groups. In this case, when forming the resist pattern, it is easy to form a resist pattern with a preferred cross-sectional shape.

[0149] (Contains -SO2- cyclic group)

[0150] Here, "-SO2-containing cyclic group" refers to a cyclic group whose ring skeleton contains a ring containing -SO2-. Specifically, it is a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. In this ring skeleton, the ring containing -SO2- is counted as the first ring. If only this ring is present, it is called a monocyclic group. If other ring structures are also present, regardless of their structure, it is called a polycyclic group. A -SO2-containing cyclic group can be either a monocyclic group or a polycyclic group.

[0151] The cyclic group containing -SO2- is particularly preferred to be a cyclic group that contains -O-SO2- in its ring skeleton, that is, a cyclic group containing a sulfonyl lactone ring in which -OS- in -O-SO2- forms part of the ring skeleton.

[0152] The number of carbon atoms containing the -SO2- cyclic group is preferably 3 to 30, more preferably 4 to 20, even more preferably 4 to 15, and particularly preferably 4 to 12. This number of carbon atoms refers to the number of carbon atoms constituting the cyclic skeleton and does not include the number of carbon atoms in the substituents.

[0153] The -SO2- cyclic group can be an aliphatic cyclic group or an aromatic cyclic group containing -SO2-. Preferably, it is an aliphatic cyclic group containing -SO2-.

[0154] Examples of aliphatic cyclic groups containing -SO2- include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which a portion of the carbon atoms constituting its ring skeleton is replaced by -SO2- or -O-SO2-. More specifically, examples include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH2- constituting its ring skeleton is replaced by -SO2-, and groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which -CH2-CH2- constituting its ring is replaced by -O-SO2-.

[0155] The alicyclic hydrocarbon ring preferably has 3 to 20 carbon atoms, more preferably 3 to 12 or less. The alicyclic hydrocarbon ring can be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane with 3 to 6 carbon atoms. Examples of such monocyclic alkane include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon ring, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane with 7 to 12 carbon atoms. Specific examples of such polycyclic alkane include adamantane, norbornane, isoboronane, tricyclodecane, and tetracyclododecane.

[0156] The -SO2- cyclic group can have substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, oxygen atom (=O), -COOR", -OC(=O)R", hydroxyalkyl, cyano, etc.

[0157] The alkyl group used as the substituent is preferably an alkyl group having 1 to 6 carbon atoms. This alkyl group is preferably straight-chain or branched. Examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, and n-hexyl. Among these, methyl or ethyl is preferred, and methyl is particularly preferred.

[0158] The alkoxy group used as the substituent is preferably an alkoxy group having 1 to 6 carbon atoms. This alkoxy group is preferably linear or branched. Specifically, examples of alkyl groups used as the substituent are groups formed by bonding an alkyl group to an oxygen atom (-O-).

[0159] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0160] Haloalkyl groups, which are substituents, can be exemplified by groups in which some or all of the hydrogen atoms of the alkyl group are replaced by the halogen atoms.

[0161] The haloalkyl group that serves as the substituent can be a group obtained by substituting part or all of the hydrogen atoms of the alkyl group mentioned above with the halogen atom. The haloalkyl group is preferably a fluoroalkyl group, and particularly preferably a perfluoroalkyl group.

[0162] In the above-mentioned -COOR” and -OC(=O)R”, R” is a straight-chain, branched or cyclic alkyl group with 1 to 15 carbon atoms.

[0163] When R” is a straight-chain or branched alkyl group, the number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 or 2.

[0164] When R” is a cyclic alkyl group, the number of carbon atoms in the cyclic alkyl group is preferably 3 to 15, more preferably 4 to 12, and particularly preferably 5 to 10. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes that can be substituted with or not substituted with fluorine atoms or fluorinated alkyl groups, or from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane, or from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0165] The hydroxyalkyl group used as the substituent is preferably a hydroxyalkyl group having 1 to 6 carbon atoms. Specifically, examples of alkyl groups used as the above-mentioned substituents include groups obtained by substituting at least one hydrogen atom of the alkyl group with a hydroxyl group.

[0166] More specifically, examples of groups represented by the following formulas (3-1) to (3-4) can be cited as -SO2- cyclic groups.

[0167] [Chemistry 19]

[0168]

[0169] (In the formula, A' represents an alkylene group, oxygen atom, or sulfur atom with a carbon number of 1 to 5 that may contain oxygen or sulfur atoms, z is an integer of 0 to 2, and R...) 10b (The R group can be alkyl, alkoxy, haloalkyl, hydroxy, -COOR", -OC(=O)R", hydroxyalkyl, or cyano, where R is a hydrogen atom or alkyl group.)

[0170] In formulas (3-1) to (3-4) above, A' is an alkylene group, oxygen atom, or sulfur atom containing 1 to 5 carbon atoms, which may contain oxygen atoms (-O-) or sulfur atoms (-S-). As the alkylene group containing 1 to 5 carbon atoms in A', it is preferably a straight-chain or branched alkylene group, and examples include methylene, ethylene, n-propylene, and isopropylene.

[0171] When the alkylene group contains an oxygen atom or a sulfur atom, examples include groups with -O- or -S- intermediates at the end of the alkylene group or between carbon atoms, such as -O-CH2-, -CH2-O-CH2-, -S-CH2-, -CH2-S-CH2-, etc. As A', an alkylene group or -O- with 1 to 5 carbon atoms is preferred, an alkylene group with 1 to 5 carbon atoms is more preferred, and a methylene group is most preferred.

[0172] z can be any of 0, 1, or 2, with 0 being the optimal value. When z is 2, multiple R... 10b They can be the same or different.

[0173] As R 10b The alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups mentioned above can be the same as the alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups that can be exemplified as substituents that can be present in the -SO2-cyclic group described above.

[0174] The following examples illustrate specific cyclic groups represented by the above formulas (3-1) to (3-4). Additionally, "Ac" in the formulas represents an acetyl group.

[0175] [Chemistry 20]

[0176]

[0177] [Chemistry 21]

[0178]

[0179] As a -SO2- cyclic group, it is preferably a group represented by the above formula (3-1), more preferably at least one selected from the group consisting of any one of the groups represented by the chemical formulas (3-1-1), (3-1-18), (3-3-1) and (3-4-1), and most preferably a group represented by the chemical formula (3-1-1).

[0180] (Contains lactone cyclic group)

[0181] "Lactone-containing cyclic group" indicates a cyclic group whose ring skeleton contains a ring (lactone ring) including -OC (=O)-. The lactone ring is designated as the first ring. In the case of only a lactone ring, it is called a monocyclic group; in the case of other ring structures, regardless of their structure, it is called a polycyclic group. Lactone-containing cyclic groups can be either monocyclic or polycyclic.

[0182] The lactone-containing cyclic group in structural unit (b-3) is not particularly limited, and any lactone-containing cyclic group can be used. Specifically, examples of lactone-containing monocyclic groups include groups obtained by removing one hydrogen atom from a four- to six-membered ring lactone, such as groups obtained by removing one hydrogen atom from β-propiolactone, groups obtained by removing one hydrogen atom from γ-butyrolactone, and groups obtained by removing one hydrogen atom from δ-pentanolactone. Furthermore, examples of lactone-containing polycyclic groups include groups obtained by removing one hydrogen atom from bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes having a lactone ring.

[0183] As for the structural unit (b-3), as long as it is a structural unit having a -SO2- cyclic group or a lactone cyclic group, the structure of other parts is not particularly limited. Preferably, at least one structural unit is selected from the group consisting of structural units (b-3-S) that are derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent, and structural units (b-3-L) that are derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent, and structural units (b-3-L) that are derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent.

[0184] [Structural Unit (b-3-S)]

[0185] As an example of the structural unit (b-3-S), more specifically, a structural unit represented by the following formula (b-S1) can be cited.

[0186] [Chemistry 22]

[0187]

[0188] (In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms.) 11b R is a ring-containing group containing -SO2-. 12b (A single bond or a divalent linker.)

[0189] In equation (b-S1), R is the same as above.

[0190] R 11b It is the same as the -SO2- cyclic group listed above.

[0191] R 12b It can be any of the single bond or divalent linker groups.

[0192] As R 12b The divalent linking group in the linking group is not particularly limited. Preferred examples include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms.

[0193] • Divalent hydrocarbon groups that may have substituents

[0194] The hydrocarbon group serving as the divalent linking group can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. This aliphatic hydrocarbon group can be saturated or unsaturated. Saturated hydrocarbon groups are generally preferred. More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, and aliphatic hydrocarbon groups containing rings in their structure.

[0195] The number of carbon atoms in the straight-chain or branched aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5.

[0196] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0197] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. As for the alkyl group in the alkyl alkylene group, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0198] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may have substituents (groups or atoms other than hydrogen atoms) that replace hydrogen atoms, or they may not have substituents. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms obtained by replacing fluorine atoms, and oxo groups (=O).

[0199] Examples of the aforementioned aliphatic hydrocarbon groups containing rings in their structure include cyclic aliphatic hydrocarbon groups containing heteroatoms in their ring structure and potentially containing substituents (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by bonding such cyclic aliphatic hydrocarbon groups to the ends of straight-chain or branched aliphatic hydrocarbon groups, and groups where the cyclic aliphatic hydrocarbon group is intermediate between straight-chain and branched aliphatic hydrocarbon groups. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups are groups identical to those described above.

[0200] The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 to 20, more preferably 3 to 12.

[0201] The cyclic aliphatic hydrocarbon group can be polycyclic or monocyclic. As a monocyclic aliphatic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms. Examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. The polycyclic alkane preferably has 7 to 12 carbon atoms. Examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0202] Cyclic aliphatic hydrocarbon groups may have substituents (groups or atoms other than hydrogen atoms) that replace hydrogen atoms, or they may not have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and oxo groups (=O).

[0203] The alkyl group used as the above-mentioned substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, and tert-butyl.

[0204] The alkoxy group used as the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, and particularly preferably methoxy and ethoxy.

[0205] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the most preferred.

[0206] Haloalkyl groups, which are substituents as described above, can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atoms described above.

[0207] In cyclic aliphatic hydrocarbon groups, a portion of the carbon atoms constituting the ring structure can be replaced by -O- or -S-. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0208] The aromatic hydrocarbon group, being a divalent hydrocarbon group, is a divalent hydrocarbon group having at least one aromatic ring and may have substituents. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0209] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing a portion of the carbon atoms in the aromatic hydrocarbon ring with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0210] As a divalent hydrocarbon group, aromatic hydrocarbon groups can specifically include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle (e.g., groups obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.).

[0211] The alkylene group bonded to the above-mentioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0212] In the aforementioned aromatic hydrocarbon group, the hydrogen atom of the aromatic hydrocarbon group can be replaced by a substituent. For example, the hydrogen atom bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, oxo groups (=O), etc.

[0213] The alkyl group used as the above-mentioned substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, n-butyl and tert-butyl.

[0214] The alkoxy group used as the above-mentioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms, and preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy, more preferably methoxy and ethoxy.

[0215] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being preferred.

[0216] Haloalkyl groups, which are substituents as described above, can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atoms.

[0217] • Divalent linking groups containing heteroatoms

[0218] In a divalent linker containing heteroatoms, heteroatoms refer to atoms other than carbon and hydrogen atoms, such as oxygen, nitrogen, sulfur, and halogen atoms.

[0219] Specifically, examples of non-hydrocarbon linking groups containing heteroatoms include -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O)2-, -S(=O)2-O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, and =N-, as well as combinations of at least one of these non-hydrocarbon linking groups with a divalent hydrocarbon group. Examples of this divalent hydrocarbon group include groups identical to the divalent hydrocarbon groups that may have substituents described above, preferably straight-chain or branched aliphatic hydrocarbon groups.

[0220] In the above, the H atoms in -NH-, -NH-, and -NH-C(=NH)- of -C(=O)-NH- can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in the substituent is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0221] As R 12b The divalent linking group in the linking group is particularly preferred to be a straight-chain or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing heteroatoms.

[0222] In R 12b When the divalent linking group is a straight-chain or branched alkylene group, the number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. Specifically, examples can be given of straight-chain or branched alkylene groups that are exemplified as straight-chain or branched aliphatic hydrocarbon groups in the description of "divalent hydrocarbon groups that may have substituents" as the divalent linking group.

[0223] In R 12b When the divalent linking group is a cyclic aliphatic hydrocarbon group, the same cyclic aliphatic hydrocarbon group as the one exemplified as "aliphatic hydrocarbon group containing a ring in the structure" in the description of "a divalent hydrocarbon group that may have substituents" as the divalent linking group can be cited.

[0224] The cyclic aliphatic hydrocarbon group is particularly preferably a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornene, isoboronane, adamantane, tricyclodecane or tetracyclododecane.

[0225] In R 12bWhen the divalent linking group is a divalent linking group containing a heteroatom, preferred examples of such linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and those with the general formula -Y. 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y2- represents the group [where Y is the group]. 1 and Y 2 Each can be independently a divalent hydrocarbon group that may have substituents, where O is an oxygen atom and m' is an integer between 0 and 3, etc.

[0226] In R 12b When the divalent linking group is -NH-, the hydrogen atom in -NH- can be replaced by a substituent such as an alkyl group or an acyl group. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0227] Formula-Y 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 -Medium,Y 1 and Y 2 Each is a divalent hydrocarbon group that may have substituents, and each can be independently represented by a substituent. Examples of such divalent hydrocarbon groups are the same groups that are "divalent hydrocarbon groups that may have substituents" as described in the description of the divalent linking groups.

[0228] As Y 1 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene and ethylene.

[0229] As Y 2 Preferably, the alkyl group is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and particularly preferably methyl.

[0230] In the formula -[Y1 -C(=O)-O] m’ -Y 2 In the group represented by -, m' is an integer of 0 to 3, preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as a group represented by the formula -[Y 1 -C(=O)-O] m’ -Y 2 - represents a group, particularly preferably represented by the formula -Y 1 -C(=O)-OY 2 - represents a group. Preferably, it is represented by the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer of 1 to 10, preferably an integer of 1 to 8, more preferably an integer of 1 to 5, further preferably 1 or 2, and most preferably 1.

[0231] For R 12b The divalent linking group in the formula, as a divalent linking group containing heteroatoms, is preferably an organic group composed of at least one non-hydrocarbon group and a divalent hydrocarbon group. Preferably, it is a straight-chain group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, and more preferably a group of the formula -Y. 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 - group, particularly preferably in the form of the formula -[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 - indicates a functional group.

[0232] As R 12b The divalent linking group in the linking group is preferably an alkylene group or a divalent linking group containing an ester bond (-C(=O)-O-).

[0233] The alkylene group is preferably a straight-chain or branched alkylene group. Examples of the straight-chain aliphatic hydrocarbon group include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-]. Preferred examples of this branched alkylene group include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-.

[0234] As a divalent linking group containing an ester bond, it is particularly preferred to have the formula: -R 13b -C(=O)-O-[where, R 13b The group is represented by a divalent linking group. That is, the structural unit (b-3-S) is preferably a structural unit represented by the following formula (b-S1-1).

[0235] [Chemistry 23]

[0236]

[0237] (where R and R) 11b The same applies to R as described above. 13b (It is a divalent linker.)

[0238] As R 13b There are no particular limitations; for example, examples related to R can be cited. 12b The same group with the same divalent linking group.

[0239] As R 13b The divalent linking group is preferably a straight-chain or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a heteroatom, more preferably a straight-chain or branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom.

[0240] As a straight-chain alkylene group, methylene or ethylene is preferred, and methylene is particularly preferred. As a branched alkylene group, alkylmethylene or alkylethylene is preferred, and -CH(CH3)-, -C(CH3)2- or -C(CH3)2CH2- is particularly preferred.

[0241] As a divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferred, and the -Y group is more preferably described above. 1 -OY 2 -、-[Y 1 -C(=O)-O] m’ -Y 2 -or-Y 1 -OC(=O)-Y 2 -. Y 1 and Y 2 Each is independently a divalent hydrocarbon group that may have substituents, and m' is an integer between 0 and 3. Preferably, -Y is preferred. 1 -OC(=O)-Y 2 -, with a particular preference for -(CH2) c -OC(=O)-(CH2) d - indicates a group. c is an integer of 1 to 5, preferably 1 or 2. d is an integer of 1 to 5, preferably 1 or 2.

[0242] As a structural unit (b-3-S), it is particularly preferred to be a structural unit represented by the following formula (b-S1-11) or (b-S1-12), and more preferably a structural unit represented by formula (b-S1-12).

[0243] [Chemistry 24]

[0244]

[0245] (where R, A', R) 10b , z and R 13b (The same applies to the above.)

[0246] In formula (b-S1-11), A' is preferably a methylene group, an oxygen atom (-O-), or a sulfur atom (-S-).

[0247] As R 13b Preferably, it is a linear or branched alkylene group or a divalent linker containing an oxygen atom. As R 13b The linear or branched alkylene groups and divalent linking groups containing oxygen atoms in the above-mentioned linear or branched alkylene groups and divalent linking groups containing oxygen atoms can be examples of groups that are the same as the linear or branched alkylene groups and divalent linking groups containing oxygen atoms.

[0248] As a structural unit represented by formula (b-S1-12), it is particularly preferred to be a structural unit represented by the following formula (b-S1-12a) or (b-S1-12b).

[0249] [Chemistry 25]

[0250]

[0251] (In the formula, R and A' are the same as above, and c to e are independent integers above 1 and below 3.)

[0252] [Structural Unit (b-3-L)]

[0253] As an example of a structural unit (b-3-L), one could exemplify R in the aforementioned equation (b-S1). 11b Structural units obtained by substitution with lactone-containing cyclic groups, more specifically, can be exemplified by structural units represented by the following formulas (b-L1) to (b-L5).

[0254] [Chemistry 26]

[0255]

[0256] (In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms; R' is independently a hydrogen atom, alkyl group, alkoxy group, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group, or cyano group, and R" is a hydrogen atom or alkyl group; R 12b (This refers to a single bond or a divalent linking group; s” is an integer between 0 and 2; A” is an alkylene group, oxygen atom, or sulfur atom containing 1 to 5 carbon atoms; r is 0 or 1.)

[0257] The R in equations (b-L1) to (b-L5) is the same as above.

[0258] As for alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl in R', examples can be made of the same groups as the aforementioned groups of alkyl, alkoxy, haloalkyl, -COOR", -OC(=O)R", and hydroxyalkyl groups that can be exemplified as substituents that contain -SO2-cyclic groups.

[0259] If industrial availability is taken into consideration, R' is preferably a hydrogen atom.

[0260] The alkyl group in "R" can be any of the following: straight-chain, branched, or cyclic.

[0261] When R” is a straight-chain or branched alkyl group, it is preferable that the number of carbon atoms is 1 to 10, and more preferably that the number of carbon atoms is 1 to 5.

[0262] When R” is a cyclic alkyl group, it is preferable to have 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples can be given by removing one or more hydrogen atoms from monocyclic alkanes that can be substituted or not substituted by fluorine atoms or fluoroalkyl groups, or from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples can be given by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane, or from polycyclic alkanes such as adamantane, norbornane, isobornane, tricyclic decane, and tetracyclic dodecane.

[0263] As "A", examples may be groups identical to A' in formula (3-1). "A" is preferably an alkylene group, an oxygen atom (-O-), or a sulfur atom (-S-) having 1 to 5 carbon atoms, more preferably an alkylene group or -O- having 1 to 5 carbon atoms. As an alkylene group having 1 to 5 carbon atoms, more preferably methylene or dimethylmethylene, and most preferably methylene.

[0264] R 12b With R in the above formula (b-S1) 12b same.

[0265] In formula (b-L1), s” is preferably 1 or 2.

[0266] The following examples illustrate specific structural units represented by equations (b-L1) to (b-L3). In the following equations, R... α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0267] [Chemistry 27]

[0268]

[0269] [Chemistry 28]

[0270]

[0271] [Chemistry 29]

[0272]

[0273] As a structural unit (b-3-L), it is preferable to select at least one from the group consisting of structural units represented by the formulas (b-L1) to (b-L5), more preferably to select at least one from the group consisting of structural units represented by the formulas (b-L1) to (b-L3), and particularly preferably to select at least one from the group consisting of structural units represented by the formulas (b-L1) or (b-L3).

[0274] Preferably, at least one is selected from the group consisting of structural units represented by the formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1), and (b-L3-5).

[0275] Furthermore, as structural unit (b-3-L), structural units represented by the following formulas (b-L6) to (b-L7) are preferred.

[0276] [Chemistry 30]

[0277]

[0278] In equations (b-L6) and (b-L7), R and R 12b Same as above.

[0279] Furthermore, in acrylic resin (B3), as a structural unit that improves the solubility of acrylic resin (B3) in alkali due to the action of acid, there are structural units represented by the following formulas (b5) to (b7) having acid-dissociable groups.

[0280] [Chemistry 31]

[0281]

[0282] In equations (b5) to (b7) above, R 14b and R 18b ~R 23b Each of the following independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a straight-chain or branched fluoroalkyl group having 1 to 6 carbon atoms. R 15b ~R 17b Each of the following groups independently represents a straight-chain or branched alkyl group having 1 to 6 carbon atoms, a straight-chain or branched fluoroalkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms. 16b and R 17bThey can bond with each other and together with the carbon atoms bonded to them, form a hydrocarbon ring with 5 to 20 carbon atoms. b It indicates an aliphatic cyclic group or alkyl group that may have substituents, p represents an integer greater than or equal to 0 and less than or equal to 4, and q represents 0 or 1.

[0283] In addition, examples of linear or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. Furthermore, fluoroalkyl refers to a group obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl groups with fluorine atoms.

[0284] Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples include groups obtained by removing one hydrogen atom from monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Particularly preferred are groups obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have substituents).

[0285] In the above R 16b and R 17b In the absence of mutual bonding to form hydrocarbon rings, from the perspective of high contrast, resolution, and coke depth width, the aforementioned R... 15b R 16b and R 17b Preferably, it is a straight-chain or branched alkyl group having 1 to 4 carbon atoms, more preferably a straight-chain or branched alkyl group having 2 to 4 carbon atoms. As described above, R... 19b R 20b R 22b R 23b Preferably, hydrogen atoms or methyl groups are used.

[0286] The above R 16b and R 17b It can also form an aliphatic cyclic group with 5 to 20 carbon atoms together with the carbon atoms bonded to both. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Particularly preferred are groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have substituents).

[0287] Furthermore, in the aforementioned R16b and R 17b When the formed aliphatic cyclic group has substituents on its cyclic skeleton, examples of such substituents include polar groups such as hydroxyl, carboxyl, cyano, and oxygen atom (=O), or straight-chain or branched alkyl groups having 1 to 4 carbon atoms. As polar groups, oxygen atom (=O) is particularly preferred.

[0288] The above Y b The group is an aliphatic cyclic group or alkyl group, and examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes or polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or polycyclic alkanes such as adamantane, norbornane, isoboronane, tricyclic decane, and tetracyclic dodecane. Groups obtained by removing one or more hydrogen atoms from adamantane are particularly preferred (and may further have substituents).

[0289] Furthermore, in the aforementioned Y b When an aliphatic cyclic group has substituents on its cyclic skeleton, examples of such substituents include polar groups such as hydroxyl, carboxyl, cyano, and oxygen atom (=O), or straight-chain or branched alkyl groups having 1 to 4 carbon atoms. As polar groups, oxygen atom (=O) is particularly preferred.

[0290] Furthermore, in Y b When the alkyl group is alkyl, it is preferred to have a straight-chain or branched alkyl group with 1 to 20 carbon atoms, and more preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferred to be alkoxyalkyl groups, and examples of such alkoxyalkyl groups include 1-methoxyethyl, 1-ethoxyethyl, 1-n-propoxyethyl, 1-isopropoxyethyl, 1-n-butoxyethyl, 1-isobutoxyethyl, 1-tert-butoxyethyl, 1-methoxypropyl, 1-ethoxypropyl, 1-methoxy-1-methyl-ethyl, 1-ethoxy-1-methylethyl, etc.

[0291] As a preferred specific example of the structural unit represented by the above formula (b5), structural units represented by the following formulas (b5-1) to (b5-33) can be cited.

[0292] [Chemistry 32]

[0293]

[0294] In the above equations (b5-1) to (b5-33), R 24b It represents a hydrogen atom or a methyl group.

[0295] As a preferred specific example of the structural unit represented by the above formula (b6), structural units represented by the following formulas (b6-1) to (b6-26) can be cited.

[0296] [Chemistry 33]

[0297]

[0298] In the above equations (b6-1) to (b6-26), R 24b It represents a hydrogen atom or a methyl group.

[0299] As a preferred specific example of the structural unit represented by the above formula (b7), structural units represented by the following formulas (b7-1) to (b7-15) can be cited.

[0300] [Chemistry 34]

[0301]

[0302] In the above equations (b7-1) to (b7-15), R 24b It represents a hydrogen atom or a methyl group.

[0303] Of the structural units represented by formulas (b5) to (b7) described above, from the viewpoint of ease of synthesis and relatively easy high sensitivity, the structural unit represented by formula (b6) is preferred. Furthermore, in the structural unit represented by formula (b6), Y is preferred. b The structural unit is an alkyl group, and R is preferred. 19b and R 20b One or both of them are alkyl structural units.

[0304] Furthermore, the acrylic resin (B3) is preferably a resin composed of a copolymer comprising structural units represented by the above formulas (b5) to (b7) and structural units derived from polymerizable compounds having ether bonds.

[0305] Examples of the aforementioned polymerizable compounds containing ether bonds include free radical polymerizable compounds such as (meth)acrylic acid derivatives containing both ether and ester bonds. Specific examples include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. Furthermore, the aforementioned polymerizable compounds containing ether bonds are preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, and methoxytriethylene glycol (meth)acrylate. These polymerizable compounds can be used alone or in combination of two or more.

[0306] Furthermore, for the purpose of appropriately controlling physical and chemical properties, other polymeric compounds can be included as structural units in acrylic resin (B3). Examples of such polymeric compounds include well-known free radical polymeric compounds and anionic polymeric compounds.

[0307] Examples of such polymeric compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives containing carboxyl groups and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, and cyclohexyl methacrylate; and hydroxyethyl methacrylate and 2-hydroxypropyl methacrylate. Alkyl esters; aryl esters of (meth)acrylate such as phenyl methacrylate and benzyl methacrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; aromatic compounds containing vinyl groups such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; aliphatic compounds containing vinyl groups such as vinyl acetate; conjugated dienes such as butadiene and isoprene; polymeric compounds containing nitrile groups such as acrylonitrile and methacrylonitrile; chlorine-containing polymeric compounds such as vinyl chloride and vinylidene chloride; polymeric compounds containing amide bonds such as acrylamide and methacrylamide.

[0308] As described above, acrylic resin (B3) may also contain structural units derived from polymeric compounds containing carboxyl groups, such as monocarboxylic acids or dicarboxylic acids. However, from the viewpoint of easily forming a resist pattern including a rectangular non-resist portion with a better cross-sectional shape, acrylic resin (B3) preferably does not substantially contain structural units derived from polymeric compounds containing carboxyl groups. Specifically, the proportion of structural units derived from polymeric compounds containing carboxyl groups in acrylic resin (B3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0309] In acrylic resin (B3), it is preferable to use an acrylic resin containing a larger amount of structural units derived from polymeric compounds having carboxyl groups in combination with an acrylic resin containing only a small amount or no structural units derived from polymeric compounds having carboxyl groups.

[0310] Furthermore, examples of polymerizable compounds include (meth)acrylates with acid-non-dissociative aliphatic polycyclic groups and vinyl-containing aromatic compounds. From the viewpoint of easy industrial availability, tricyclic decyl, adamantyl, tetracyclic dodecyl, isobornyl, norbornyl, etc., are particularly preferred as acid-non-dissociative aliphatic polycyclic groups. These aliphatic polycyclic groups can have straight-chain or branched alkyl groups with 1 to 5 carbon atoms as substituents.

[0311] As a type of (meth)acrylate with an aliphatic polycyclic group that is acid-non-dissociable, specifically, compounds with structures of the following formulas (b8-1) to (b8-5) can be exemplified.

[0312] [Chemistry 35]

[0313]

[0314] In the above equations (b8-1) to (b8-5), R 25b It represents a hydrogen atom or a methyl group.

[0315] When the acrylic resin (B3) contains structural units (b-3) containing -SO2- cyclic groups or lactone cyclic groups, the content of structural units (b-3) in the acrylic resin (B3) is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less, and most preferably 10% by mass or more and 30% by mass or less. When the positive photosensitive composition contains structural units (b-3) in amounts within the above range, it is easy to achieve both good developability and good pattern shape.

[0316] Furthermore, the acrylic resin (B3) preferably contains 5% or more by mass, more preferably 10% or more by mass, and particularly preferably 10% or more and 50% or less by mass of structural units represented by the above formulas (b5) to (b7).

[0317] The acrylic resin (B3) preferably contains structural units derived from the polymerizable compound having ether bonds described above. The content of structural units derived from the polymerizable compound having ether bonds in the acrylic resin (B3) is preferably 0% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 40% by mass or less, and even more preferably 5% by mass or more and 30% by mass or less.

[0318] The acrylic resin (B3) preferably contains structural units derived from the above-mentioned aliphatic polycyclic groups with acid non-dissociation properties of (meth)acrylates. In the acrylic resin (B3), the content of structural units derived from aliphatic polycyclic groups with acid non-dissociation properties of (meth)acrylates is preferably 0% by mass or more than 60% by mass, more preferably 5% by mass or more than 50% by mass, and even more preferably 5% by mass or more than 30% by mass.

[0319] As long as the positive photosensitive composition contains a specified amount of acrylic resin (B3), acrylic resins other than the acrylic resin (B3) described above can also be used as resin (B). As for such acrylic resins other than acrylic resin (B3), there are no particular limitations as long as they contain structural units represented by the formulas (b5) to (b7) described above.

[0320] The polystyrene equivalent weight-average molecular weight of the resin (B) described above is preferably 10,000 to 600,000, more preferably 20,000 to 400,000, and even more preferably 30,000 to 300,000. By setting such a weight-average molecular weight, sufficient strength of the photosensitive layer composed of the positive photosensitive composition can be maintained without reducing the peelability of the photosensitive layer from the substrate, thereby preventing the expansion or cracking of the profile during plating.

[0321] Furthermore, the molecular weight distribution coefficient of resin (B) is preferably 1.05 or higher. Here, the molecular weight distribution coefficient refers to the value obtained by dividing the mass-average molecular weight by the number-average molecular weight. By setting such a molecular weight distribution coefficient, the desired stress resistance relative to the plating can be obtained, or the problem of the metal layer obtained due to the plating process becoming prone to expansion can be avoided.

[0322] The content of resin (B) is preferably set to 5% by mass or more and 60% by mass or less relative to the total mass of the positive photosensitive composition.

[0323] Furthermore, the content of resin (B) relative to the total solids content of the positive photosensitive composition is preferably 5% by mass or more and 98% by mass or less, more preferably 10% by mass or more and 95% by mass or less.

[0324] <Sulfur-containing compounds (C)>

[0325] The sulfur-containing compound (C) contained in the positive photosensitive composition is solid at room temperature (25°C).

[0326] Sulfur-containing compounds (C) are, for example, compounds containing sulfur atoms that can coordinate with metals.

[0327] When a resist pattern is formed on a surface made of metal such as Cu as a mold for plating, defects such as foot shape defects are easily produced. However, when the positive photosensitive composition contains a sulfur-containing compound (C), the occurrence of foot shape defects is easily suppressed even when the resist pattern is formed on a metal surface in the substrate. In addition, "foot" refers to the phenomenon that the bottom width of the non-resist portion is narrower than the top width in the non-resist portion because the resist portion protrudes towards the non-resist portion side near the contact surface between the resist portion and the resist pattern on the substrate surface.

[0328] However, when using photosensitive compositions containing sulfur-containing compounds (C) that are solid at room temperature, foreign matter often exists in the photosensitive composition or in the resulting resist pattern. This foreign matter originates from the sulfur-containing compounds contained in the chemically amplified resist composition. If foreign matter is present in the resist pattern, it is difficult to form the desired shape of the plating or etching pattern when using the resist pattern as a mold or etching mask for forming plating patterns. Furthermore, when removing foreign matter originating from sulfur-containing compounds by filtration, the desired effect on improving the shape of the resist pattern may be compromised due to a reduction in the sulfur-containing compound content in the chemically amplified resist composition.

[0329] As will be described in detail later, in the manufacturing method of the present invention, since a sulfur-containing compound (C) is dissolved in a specific solvent (S1) in advance to prepare a sulfur-containing compound (C) solution, and the sulfur-containing compound (C) solution is mixed with an acid-generating agent (A) and a solvent (S2), a photosensitive composition in which foreign matter from the sulfur-containing compound (C) is reduced can be manufactured even though the sulfur-containing compound (C) is solid at room temperature.

[0330] As sulfur-containing compounds (C), examples can be given of compounds and their tautomers represented by the following formulas (c1-1) or (c1-2).

[0331] [Chemistry 36]

[0332]

[0333] In equations (c1-1) and (c1-2),

[0334] Ring A is a monocyclic ring with 4 to 8 constituent atoms or a polycyclic ring with 5 to 20 constituent atoms.

[0335] X 1c For -CR 11c R 12c -、-NR 13c -, -O-, -S-, -Se-, -Te-, =CR 14c -or = N-,

[0336] X 2c For -CR 11c = or -N=,

[0337] R 11c R 12c R 13c and R 14c Each of the following groups can be independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms that may have substituents, an alkenyl group having 1 to 8 carbon atoms that may have substituents, an alkynyl group having 1 to 8 carbon atoms that may have substituents, or an aromatic group or carboxyl group having 4 to 20 carbon atoms that may have substituents.

[0338] The tautomer of the compound represented by formula (c1-1) above is, for example, the compound represented by formula (c1-1') below. The tautomer of the compound represented by formula (c1-2) above is, for example, the compound represented by formula (c1-2') below.

[0339] [Chemistry 37]

[0340]

[0341] (In equations (c1-1' and (c1-2'), rings A and X) 1c R 11c R 12c R 13c and R 14c X is the same as equations (c1-1) and (c1-2) respectively. 3c H is -CR 11c H- or -NH-.

[0342] Ring A can be either an aromatic heterocycle or an aliphatic heterocycle.

[0343] When ring A is a single ring, the number of ring constituent atoms is preferably 5 or more but less than 7, more preferably 5 or 6.

[0344] Specific examples of ring A as a monocyclic ring include pyrrole ring, imidazoline ring, imidazoline ring, triazole ring, pyridine ring, pyrimidine ring, pyridazine ring, pyrazine ring, triazine ring, and thiadiazole ring.

[0345] When ring A is a multi-ring, the number of single rings constituting the multi-ring is preferably 1 to 3, more preferably 1 or 2.

[0346] Specific examples of polycyclic rings include indole rings, benzimidazole rings, purine rings, quinoline rings, isoquinoline rings, quinazoline rings, naphthidine rings, and pteridine rings.

[0347] Ring A can have substituents. Examples of substituents that ring A can have include hydroxyl, amino, amide, imide, carboxyl, alkoxy, carboxylic acid ester, halogen atom, saturated or unsaturated hydrocarbon group, and aromatic groups that may have substituents such as hydroxyl.

[0348] As R 11c R 12c R 13c and R 14c Alkyl groups having 1 to 8 carbon atoms can be substituted, and examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, etc.

[0349] As R 11c R 12c R 13c and R 14c Alkenyl groups can have 1 to 8 carbon atoms as substituents, such as 3-butenyl, pentenyl, hexenyl, heptenyl, octenyl, etc.

[0350] As R 11c R 12c R 13c and R 14c Alkyne groups that can have 1 to 8 carbon atoms as substituents include pentyynyl, hexynyl, heptynyl, octyynyl, etc.

[0351] As R 11c R 12c R 13c and R 14c The aromatic group may have a substituent with 4 to 20 carbon atoms, such as aryl groups like phenyl and naphthyl, or heteroaryl groups like furanyl and thiophene.

[0352] As R 11c R 12c R 13c and R 14cAlkyl groups with 1 to 8 carbon atoms, alkenyl groups with 1 to 8 carbon atoms, alkynyl groups with 1 to 8 carbon atoms, and aromatic groups with 4 to 20 carbon atoms may have substituents, such as halogen atoms, cyano groups, oxoalkoxy groups, hydroxyl groups, amino groups, nitro groups, aryl groups, and alkyl groups obtained by substitution with halogen atoms.

[0353] In equation (c1-1), X 1c Preferred is -NR 13c - or = N-.

[0354] Examples of compounds represented by formula (c1-1) or (c1-2) include mercaptopyridine, mercaptopyrimidine, mercaptopyrazine, mercaptopyrazine, mercaptotriazine, mercaptoimazole, mercaptoinazole, mercaptotriazole, mercaptothiadiazole, mercaptobenzimidazole, etc., which can be substituted respectively.

[0355] Specific examples of compounds represented by formula (c1-1) or (c1-2) include 2-mercaptopyridine, 2-mercaptonicotinic acid, 2-mercaptopyrimidine, 4-mercaptopyrimidine, 3-mercaptopyridazine, 2-mercaptopyridine, 2-mercapto-1,3,5-triazine, 3-mercapto-1,2,4-triazine, 2-mercaptoimidazole, 2-mercapto-1,3,4-thiadiazole, 2-mercaptobenzimidazole, and compounds represented by the following formulas.

[0356] [Chemistry 38]

[0357]

[0358] Examples of compounds represented by formula (c1-1') or (c1-2') include 2-thiouracil, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-methoxy-2-thiouracil, and 5-n-butoxy-2-thiouracil. 5-Methoxy-6-n-propyl-2-thiourea pyrimidine, 5-bromo-2-thiourea pyrimidine, 5-chloro-2-thiourea pyrimidine, 5-fluoro-2-thiourea pyrimidine, 5-amino-2-thiourea pyrimidine, 5-amino-6-methyl-2-thiourea pyrimidine, 5-amino-6-phenyl-2-thiourea pyrimidine, 5,6-diamino-2-thiourea pyrimidine, 5-allyl-2-thiourea pyrimidine, 5-allyl-3-ethyl-2-thiourea pyrimidine, 5-allyl-6-phenyl-2-thiourea pyrimidine, 5-benzyl-2-thiourea pyrimidine, 5-benzyl-6-methyl-2-thiourea pyrimidine, 5-acetamide-2-thiourea pyrimidine, 6-methyl-5-nitro-2-thiourea pyrimidine, 6-amino-2-thiourea pyrimidine, 6-amino- 5-Methyl-2-thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetamide-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil Thiourea pyrimidine derivatives, including 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-tert-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetamide-5-ethyl-2-thiouracil, 6-eicosyl-5-allyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, and 6-(2-bromoethyl)-2-thiouracil.

[0359] As sulfur-containing compounds (C), other compounds represented by the following formula (c2) can also be cited.

[0360] [Chemistry 39]

[0361]

[0362] (in formula (c2),)

[0363] Y 1c and Y 2c Each can be independently a nitrogen atom or a carbon atom.

[0364] R 21c and R 22c Each group can be independently composed of a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an alicyclic hydrocarbon group with 3 to 18 carbon atoms.

[0365] R 23c The following groups are included: aliphatic hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, and -SR. 24c or -NR 25c R 26c ,

[0366] R 24c R 25c and R 26c R is independently a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an acyl group with 1 to 12 carbon atoms. 25c and R 26c The hydrogen atoms of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and acyl groups can be replaced by hydroxyl groups.

[0367] n and m are independently 0 or 1, in Y 1c When the atom is nitrogen, n is 0, and in Y 1c When the atom is carbon, n is 1, and in Y 2c When the atom is nitrogen, m is 0, and in Y 2c (In the case of carbon atoms, m is 1.)

[0368] As R 21c and R 22c Alkyl groups with 1 to 10 carbon atoms are aliphatic hydrocarbon groups, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, and octyl.

[0369] As R 21cand R 22c Aromatic hydrocarbon groups with 6 to 14 carbon atoms include phenyl, naphthyl, anthracene, p-methylphenyl, p-tert-butylphenyl, p-adamantylphenyl, tolyl, xylyl, isopropylphenyl, mesitylene, biphenyl, phenanthrene, 2,6-diethylphenyl, 2-methyl-6-ethylphenyl, etc.

[0370] As R 21c and R 22c Alicyclic hydrocarbon groups with 3 to 18 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornel.

[0371] As R 23c Aliphatic hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, and alicyclic hydrocarbon groups with 3 to 18 carbon atoms can be cited as examples of R. 21c and R 22c It is the same as an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, and an alicyclic hydrocarbon group with 3 to 18 carbon atoms.

[0372] As R 24c R 25c and R 26c Aliphatic hydrocarbon groups with 1 to 10 carbon atoms and aromatic hydrocarbon groups with 6 to 14 carbon atoms can be exemplified as R. 21c and R 22c It is the same as an aliphatic hydrocarbon group with 1 to 10 carbon atoms and an aromatic hydrocarbon group with 6 to 14 carbon atoms.

[0373] As R 24c R 25c and R 26c Alicyclic hydrocarbon groups with 3 to 10 carbon atoms include monocyclic alicyclic hydrocarbon groups such as cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; as well as polycyclic alicyclic hydrocarbon groups such as decahydronaphthyl, adamantyl, and norbornel.

[0374] As R 24c R 25c and R 26c Acyl groups with 1 to 12 carbon atoms include acetyl, propionyl, butyryl, valerate, hexylcarbonyl, heptylcarbonyl, octylcarbonyl, decylcarbonyl, dodecylcarbonyl, and benzoyl.

[0375] In equation (c2), Y 1cand Y 2c Nitrogen atoms are preferred.

[0376] As a specific example of a compound represented by formula (c2), a compound represented by the following formula can be cited.

[0377] [Chemistry 40]

[0378]

[0379] The sulfur-containing compound (C) is preferably used in a range of 0.01 to 5 parts by mass relative to the total mass of resin (B) and the alkali-soluble resin (D) described later, more preferably in a range of 0.01 to 3 parts by mass, and even more preferably in a range of 0.03 to 2 parts by mass.

[0380] Alternatively, it may contain sulfur-containing compounds that are liquid at room temperature, but the content of sulfur-containing compounds that are solid at room temperature (C) is preferably 50% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass, relative to the total of sulfur-containing compounds that are solid at room temperature and sulfur-containing compounds that are liquid at room temperature.

[0381] <Alkali-soluble resin (D)>

[0382] To improve crack resistance, the positive photosensitive composition preferably also contains an alkali-soluble resin (D). Here, an alkali-soluble resin refers to a resin film with a thickness of 1 μm formed on a substrate using a 20% by weight resin solution (solvent: propylene glycol monomethyl ether acetate), which dissolves at least 0.01 μm when immersed in a 2.38% by weight TMAH aqueous solution for 1 minute. Preferably, the alkali-soluble resin (D) is at least one resin selected from the group consisting of phenolic varnish resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

[0383] [Phenolic varnish resin (D1)]

[0384] Phenolic varnish resins are obtained, for example, by adding and condensing aromatic compounds (hereinafter referred to as "phenols") with aldehydes under an acid catalyst.

[0385] Examples of the aforementioned phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, p-butylphenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4,5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, phloroglucinol, phloroglucinol, hydroxybiphenyl, bisphenol A, gallic acid, gallic ester, α-naphthol, β-naphthol, etc.

[0386] Examples of aldehydes mentioned above include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, and acetaldehyde.

[0387] There are no particular limitations on the catalyst used in addition condensation reactions; for example, acid catalysts such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid can be used.

[0388] In addition, the flexibility of phenolic varnish resin can be further improved by using o-cresol, replacing the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes.

[0389] The mass-average molecular weight of the phenolic varnish resin (D1) is not particularly limited within the scope of the present invention without hindering the purpose of the present invention, but is preferably 1,000 or more and 50,000 or less.

[0390] [Polyhydroxystyrene resin (D2)]

[0391] Examples of hydroxystyrene compounds that constitute polyhydroxystyrene resin (D2) include p-hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene.

[0392] Furthermore, the polyhydroxystyrene resin (D2) is preferably a copolymer with styrene resin. Examples of styrene compounds constituting such a styrene resin include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, α-methylstyrene, etc.

[0393] The mass-average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited within the scope of the present invention without hindering the purpose of the present invention, but is preferably 1,000 or more and 50,000 or less.

[0394] [Acrylic resin (D3)]

[0395] As an acrylic resin (D3), it is preferred to contain structural units derived from polymeric compounds having ether bonds and structural units derived from polymeric compounds having carboxyl groups.

[0396] Examples of polymerizable compounds containing ether bonds include 2-methoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and other (meth)acrylate derivatives containing both ether and ester bonds. 2-methoxyethyl acrylate and methoxytriethylene glycol acrylate are preferred among the aforementioned polymerizable compounds containing ether bonds. These polymerizable compounds can be used alone or in combination of two or more.

[0397] Examples of the aforementioned carboxyl-containing polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; and compounds containing both carboxyl groups and ester bonds, such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid. Acrylic acid and methacrylic acid are preferred among these carboxyl-containing polymerizable compounds. These polymerizable compounds can be used alone or in combination of two or more.

[0398] The mass-average molecular weight of the acrylic resin (D3) is not particularly limited within the range that does not impede the purpose of the present invention, but is preferably 50,000 to 800,000.

[0399] When the total amount of the above-mentioned resin (B) and alkali-soluble resin (D) is set to 100 parts by mass, the content of alkali-soluble resin (D) is preferably 0 parts by mass or more than 80 parts by mass, and more preferably 0 parts by mass or more than 60 parts by mass. By setting the content of alkali-soluble resin (D) within the above range, there is a tendency to improve crack resistance and prevent film reduction during development.

[0400] <Acid Diffusion Inhibitor (F)>

[0401] To improve the shape of the resist pattern or the static stability of the photosensitive resin film, the positive photosensitive composition preferably also contains an acid diffusion inhibitor (F). As the acid diffusion inhibitor (F), a nitrogen-containing compound (F1) is preferred, and it may further contain an organic carboxylic acid, or an oxyacid of phosphorus or its derivative (F2) as needed.

[0402] [Nitrogen-containing compounds (F1)]

[0403] Examples of nitrogen-containing compounds (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, and acetamide. N-methylacetamide, N,N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazolium, 8-hydroxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tris(2-pyridyl)triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine, etc. These can be used alone or in combination of two or more.

[0404] In addition, commercially available hindered amine compounds such as ADK STAB LA-52, ADK STAB LA-57, ADK STAB LA-63P, ADK STAB LA-68, ADK STAB LA-72, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-81, ADK STAB LA-82, and ADK STAB LA-87 (all manufactured by ADEKA) or 4-hydroxy-1,2,2,6,6-pentamethylpiperidine derivatives, or pyridines obtained by substituting the 2,6-positions of 2,6-diphenylpyridine and 2,6-di-tert-butylpyridine with substituents such as hydrocarbon groups, can also be used as nitrogen-containing compounds (F1).

[0405] The nitrogen-containing compound (F1) is typically used in the range of 0 to 5 parts by mass relative to the total mass of the above-mentioned resin (B) and the above-mentioned alkali-soluble resin (D) of 100 parts by mass, and is particularly preferably used in the range of 0 to 3 parts by mass.

[0406] [Organic carboxylic acids, or oxyacids of phosphorus or their derivatives (F2)]

[0407] Among organic carboxylic acids, or oxyacids of phosphorus or their derivatives (F2), the organic carboxylic acid is preferably malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc., and particularly preferably salicylic acid.

[0408] Examples of oxyacids of phosphorus or their derivatives include phosphoric acid, di-n-butyl phosphate, diphenyl phosphate, and other phosphoric acids and their ester derivatives; phosphonic acids, dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and their ester derivatives; and hypophosphonic acids, phenylhydantoin, and their ester derivatives. Among these, phosphonic acids are particularly preferred. These can be used alone or in combination of two or more.

[0409] The organic carboxylic acid, or an oxyacid of phosphorus or its derivative (F2) is used in a range of 0 to 5 parts by mass relative to the total mass of the above-mentioned resin (B) and the above-mentioned alkali-soluble resin (D) of 100 parts by mass, and is particularly preferred to be used in a range of 0 to 3 parts by mass.

[0410] In addition, in order to form a salt and stabilize it, the organic carboxylic acid, or the oxyacid of phosphorus or its derivative (F2) is preferably used in the same amount as the nitrogen-containing compound (F1) mentioned above.

[0411] <Organic Solvents (S)>

[0412] The photosensitive composition contains an organic solvent (S). Furthermore, in this invention, the photosensitive composition contains a polarity term δp of the Hansen solubility parameter of 10 (MPa). 0.5 The solvent (S1) and the solvent (S2) different from the solvent (S1) are used as organic solvents (S).

[0413] In the manufacturing method of the present invention, a sulfur-containing compound (C) is dissolved in advance in a solution with a polarity term δp of the Hansen solubility parameter of 10 MPa. 0.5 The solvent (S1) obtained above is used to prepare a solution of sulfur-containing compound (C) (premixed liquid) as a solution, and the solution of sulfur-containing compound (C) is mixed with an acid-producing agent (A) and a solvent (S2), thereby enabling the production of a photosensitive composition in which foreign matter from sulfur-containing compound (C) is reduced.

[0414] The polar term of the Hansen solubility parameter (the term representing the energy generated by the interaction between dipoles), δp, can be obtained using software developed by Charles Hansen et al. (software name: Hansen Solubility Parameter in Practice (HSPiP)).

[0415] The polarity term δp of Hansen's solubility parameter is preferably 12 (MPa). 0.5 ) or more, more preferably 16 (MPa) 0.5 )above.

[0416] The boiling point of the solvent (S1) is preferably 180°C or higher, more preferably 200°C or higher. Furthermore, the boiling point is the boiling point under atmospheric pressure.

[0417] As a solvent (S1), γ-butyrolactone (δp: 16.6 MPa) can be cited as an example. 0.5 Boiling point: 204~205℃), dimethyl sulfoxide (δp: 16.4MPa) 0.5 Boiling point: 189℃), N-methyl-2-pyrrolidone (δp: 12.3MPa) 0.5 (Boiling point: 202℃).

[0418] The type of solvent (S2) is not particularly limited without hindering the purpose of the present invention, and can be appropriately selected and used from organic solvents conventionally used for positive photosensitive compositions. The desired photosensitive composition can be prepared using organic solvents conventionally used for positive photosensitive compositions.

[0419] Specific examples of organic solvents (S2) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isopentyl ketone, and 2-heptanone; polyols such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether of ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, and dipropylene glycol monoacetate, as well as their derivatives; cyclic ethers such as dioxane; ethyl formate, methyl lactate, ethyl lactate, and acetic acid. Esters such as methyl esters, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxylate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxybutylacetate, and methyl-3-methoxybutylacetate; aromatic hydrocarbons such as toluene and xylene. These can be used alone or in combination of two or more.

[0420] In addition, specific examples of organic solvents (S2) include N-methylformamide, N,N-dimethylformamide, N-methylformaniline, N-methylacetamide, benzyl ethyl ether, dihexyl ether, acetone-based acetone, isophorone, hexanoic acid, octanoic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, etc.

[0421] In the photosensitive composition, the content of solvent (S1) relative to the total mass of solvent (S1) and solvent (S2) is preferably more than 0% by mass and less than 20% by mass, more preferably more than 0% by mass and less than 10% by mass, and even more preferably more than 0% by mass and less than 5% by mass. Furthermore, a photosensitive composition in which the content of solvent (S1) relative to the total mass of solvent (S1) and solvent (S2) is more than 0% by mass and less than 5% by mass is the chemically amplified photosensitive composition of the present invention, and is a novel photosensitive composition.

[0422] In the photosensitive composition, the content of the organic solvent (S), i.e., the total mass of solvent (S1) and solvent (S2), is not particularly limited to a extent that does not impair the purpose of the present invention. When the photosensitive composition is used to produce a thick film such that the thickness of the photosensitive layer obtained by spin coating or the like is 2 μm or more, the organic solvent (S) is preferably used to make the concentration of the solid component of the photosensitive composition in the range of 30% by mass or more, more preferably 30% by mass or more and 55% by mass or less.

[0423] <Other Ingredients>

[0424] To improve plasticity, the photosensitive composition may also contain a polyethylene resin. Specific examples of polyethylene resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylphenol, and copolymers thereof. From the viewpoint of a lower glass transition point, polyvinyl methyl ether is preferred.

[0425] The photosensitive composition may also contain Lewis acid compounds. By including Lewis acid compounds in the photosensitive composition, it is easy to obtain a highly sensitive photosensitive composition, and it is easier to use a positive photosensitive composition to form a resist pattern with a rectangular cross-sectional shape.

[0426] Furthermore, when using photosensitive compositions to form patterns, if the time required for each step in the pattern-forming process or the time required between steps is long, it can sometimes result in the pattern being difficult to form the desired shape or size, or in adverse effects such as deterioration of developability. However, by incorporating Lewis acid compounds into the photosensitive composition, such adverse effects on pattern shape or developability can be mitigated, and the process margin can be widened.

[0427] Here, Lewis acidic compounds are defined as "compounds that have empty orbitals capable of accepting at least one electron pair and that act as electron pair acceptors".

[0428] As a Lewis acid compound, there are no particular limitations as long as the compound meets the above definition and is recognized by those skilled in the art as a Lewis acid compound. Preferably, the compound used is not a Brønsted acid (protic acid).

[0429] Specific examples of Lewis acidic compounds include boron fluoride, boron fluoride ether complexes (e.g., BF3-Et2O, BF3-Me2O, BF3-THF, etc., where Et is ethyl, Me is methyl, and THF is tetrahydrofuran), organoboron compounds (e.g., tri-n-octyl borate, tri-n-butyl borate, triphenyl borate, and triphenylboron), titanium chloride, aluminum chloride, aluminum bromide, gallium chloride, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethanesulfonate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, nickel cyanide, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate, etc.

[0430] In addition, other specific examples of Lewis acidic compounds include chlorides, bromides, sulfates, nitrates, carboxylates, or trifluoromethanesulfonates of rare earth metals; cobalt chloride, ferrous chloride, and yttrium chloride, etc.

[0431] Here, rare earth metal elements include, for example, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

[0432] From the perspective of easy availability and the good effects brought about by its addition, Lewis acid compounds are preferably Lewis acid compounds containing elements of Group 13 of the periodic table.

[0433] Here, boron, aluminum, gallium, indium, and thallium are examples of elements in Group 13 of the periodic table.

[0434] Among the elements in Group 13 of the periodic table, boron is preferred from the perspective of ease of obtaining Lewis acid compounds and particularly excellent addition effect. That is, Lewis acid compounds preferably contain boron.

[0435] Examples of boron-containing Lewis acid compounds include boron fluoride, boron fluoride ether complexes, boron chloride, boron bromide, and various organoboron compounds. Among boron-containing Lewis acid compounds, organoboron compounds are preferred from the perspective of having a lower halogen atom content and facilitating the application of photosensitive compositions to applications requiring low halogen content.

[0436] As a preferred example of an organoboron compound, a boron compound represented by the following formula (f1) can be cited.

[0437] B(R f1 ) t1 (OR f2 ) (3-t1) ...(f1)

[0438] (In formula (f1), R) f1 and R f2 Each is independently a hydrocarbon group having 1 to 20 carbon atoms, and the hydrocarbon group may have one or more substituents, where t1 is an integer between 0 and 3, and multiple R groups are present. f1 In the case of multiple R f1 Two of them can bond together to form a ring, and there are multiple ORs. f2 In the case of multiple ORs f2 Two of them can bond together to form a ring.

[0439] The photosensitive composition preferably contains one or more boron compounds represented by the above formula (f1) as Lewis acid compounds.

[0440] In equation (f1), in R f1 and R f2 When the group is a hydrocarbon group, the number of carbon atoms in the hydrocarbon group is 1 to 20. A hydrocarbon group with 1 to 20 carbon atoms can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group composed of aliphatic and aromatic groups.

[0441] As a hydrocarbon group with 1 to 20 carbon atoms, a saturated aliphatic or aromatic hydrocarbon group is preferred. As R f1 and R f2 The number of carbon atoms in the hydrocarbon group is preferably 1 to 10. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms is more preferably 1 to 6, and particularly preferably 1 to 4.

[0442] As R f1 and R f2 The hydrocarbon group can be a saturated hydrocarbon group or an unsaturated hydrocarbon group, but a saturated hydrocarbon group is preferred.

[0443] As R f1 and R f2 When the hydrocarbon group is an aliphatic hydrocarbon group, the aliphatic hydrocarbon group can be straight-chain, branched, cyclic, or a combination of these structures.

[0444] Preferred examples of aromatic hydrocarbon groups include phenyl, naphth-1-yl, naphth-2-yl, 4-phenylphenyl, 3-phenylphenyl, and 2-phenylphenyl. Among these, phenyl is preferred.

[0445] Alkyl groups are preferred as saturated aliphatic hydrocarbon groups. Specific examples of preferred alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, and n-decyl.

[0446] As R f1 and R f2 The hydrocarbon group can have more than one substituent. Examples of substituents include halogen atoms, hydroxyl groups, alkyl groups, aralkyl groups, alkoxy groups, cycloalkyloxy groups, aryloxy groups, aralkyloxy groups, alkylthio groups, cycloalkylthio groups, arylthio groups, arylalkylthio groups, acyl groups, acyloxy groups, acylthio groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, amino groups, N-monosubstituted amino groups, N,N-disubstituted amino groups, carbamoyl groups (-CO-NH2), N-monosubstituted carbamoyl groups, N,N-disubstituted carbamoyl groups, nitro groups, and cyano groups.

[0447] The number of carbon atoms in the substituents is not particularly limited as long as it does not impede the purpose of the present invention, but is preferably 1 to 10, more preferably 1 to 6.

[0448] As a preferred specific example of an organoboron compound represented by the above formula (f1), the following compounds can be cited. In addition, in the following formulas, Pen represents pentyl, Hex represents hexyl, Hep represents heptyl, Oct represents octyl, Non represents nonyl, and Dec represents decyl.

[0449] [Chemistry 41]

[0450]

[0451] [Chemistry 42]

[0452]

[0453] [Chemistry 43]

[0454]

[0455] [Chemistry 44]

[0456]

[0457] [Chemistry 45]

[0458]

[0459] Relative to the total mass of the above-mentioned resin (B) and the above-mentioned alkali-soluble resin (D) of 100 parts by mass, it is preferable to use the Lewis acid compound in the range of 0.01 parts by mass to 5 parts by mass, more preferably in the range of 0.01 parts by mass to 3 parts by mass, and even more preferably in the range of 0.05 parts by mass to 2 parts by mass.

[0460] Furthermore, when the photosensitive composition is used to form a pattern for a mold used to form a plated model, the photosensitive composition may also contain an adhesive aid in order to improve the adhesion between the mold formed using the photosensitive composition and the metal substrate.

[0461] In addition, to improve coatability, defoaming properties, leveling properties, etc., the photosensitive composition may also contain a surfactant. As a surfactant, fluorinated surfactants or organosilicon surfactants are preferred, for example.

[0462] Specific examples of fluorinated surfactants include commercially available fluorinated surfactants such as BM-1000, BM-1100 (both manufactured by BM Chemicals), MEGAFAC F142D, MEGAFAC F172, MEGAFAC F173, MEGAFAC F183 (all manufactured by Dai Nippon Ink Chemical Industry Co., Ltd.), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surflon S-113, Surflon S-131, Surflon S-141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicones Co., Ltd.), but are not limited to these.

[0463] As organosilicon surfactants, unmodified organosilicon surfactants, polyether-modified organosilicon surfactants, polyester-modified organosilicon surfactants, alkyl-modified organosilicon surfactants, aralkyl-modified organosilicon surfactants, and reactive organosilicon surfactants are preferably used.

[0464] As a silicone surfactant, commercially available silicone surfactants can be used. Specific examples of commercially available silicone surfactants include PAINTADD M (manufactured by Toray Industries, Inc.), Tepika K1000, Tepika K2000, Tepika K5000 (all manufactured by Takachiho Industries, Inc.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by BYK Chemical Co., Ltd.).

[0465] In addition, the photosensitive composition may also contain an acid or anhydride in order to fine-tune its solubility relative to the developer.

[0466] Specific examples of acids and anhydrides include monocarboxylic acids such as acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxy monocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; and oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid, and 1... Polycarboxylic acids such as 2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, and 1,2,5,8-naphthalenetetracarboxylic acid; and anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarboxylic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, 1,2,3,4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol ditriphenyltrihydride, and glycerol trimellitic anhydride.

[0467] In addition, to improve sensitivity, the photosensitizing composition may also contain known sensitizers.

[0468] <Manufacturing Method>

[0469] In the method for manufacturing the photosensitive composition of the present invention, the above-mentioned photosensitive composition is manufactured. Furthermore, the method for manufacturing the photosensitive composition is characterized by comprising: a step of preparing a sulfur-containing compound (C) solution by dissolving a sulfur-containing compound (C) in a solvent (S1); and a step of mixing the sulfur-containing compound (C) solution, an acid-generating agent (A), and a solvent (S2).

[0470] In the process of preparing a sulfur-containing compound (C) solution by dissolving a sulfur-containing compound (C) in a solvent (S1), any solvent capable of dissolving the sulfur-containing compound (C) is acceptable. As the solvent for dissolving the sulfur-containing compound (C), only solvent (S1) may be used; alternatively, both solvent (S1) and solvent (S2) may be used simultaneously. The content of solution (S1) in the solvent for dissolving the sulfur-containing compound (C), i.e., the solvent contained in the sulfur-containing compound (C) solution, is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 85% by mass or more, and particularly preferably 100% by mass, relative to the total content of solvent (S1) and solvent (S2).

[0471] In addition, the sulfur-containing compound (C) solution obtained in this process is a premixed solution for preparing the chemically amplified photosensitive composition of the present invention.

[0472] Next, the obtained sulfur-containing compound (C) solution (premixed solution for preparing chemically magnified photosensitive composition) is mixed with acid-generating agent (A) and solvent (S2). Additionally, resin (B) and alkali-soluble resin (D), and other components as needed, are also mixed in.

[0473] There is no particular limitation on the order of mixing these components. For example, the sulfur-containing compound (C) solution can be mixed with the acid-producing agent (A) and the solvent (S2) at the same time. Alternatively, the acid-producing agent (A) can be mixed after the sulfur-containing compound (C) solution and the solvent (S2) are mixed.

[0474] In this way, in the present invention, since a sulfur-containing compound (C) solution is prepared by dissolving the sulfur-containing compound (C) in a specific solvent (S1) beforehand, and this sulfur-containing compound (C) solution is mixed with an acid-generating agent (A) and a solvent (S2), the resulting photosensitive composition does not produce any dissolved residues of the sulfur-containing compound (C). Furthermore, since the sulfur-containing compound (C) is dissolved in the specific solvent (S1), it is difficult for the sulfur-containing compound (C) to precipitate even after subsequent mixing with other components. Therefore, despite containing a sulfur-containing compound (C) that is solid at room temperature, the photosensitive composition exhibits reduced foreign matter originating from the sulfur-containing compound.

[0475] By using a photosensitive composition that reduces foreign matter, it is possible to form a resist pattern that reduces foreign matter.

[0476] Furthermore, if the resist pattern that reduces foreign matter is used as a mold or etching mask for forming the plated shape, the desired shape of the plated shape or etching formation can be formed.

[0477] Furthermore, even if the photosensitive composition is filtered, since the sulfur-containing compounds (C) have already dissolved and cannot be removed by filtration, there is no need to worry about a reduction in the content of sulfur-containing compounds (C) in the photosensitive composition.

[0478] Furthermore, due to the use of a specific solvent (S1), sulfur-containing compounds (C) can be dissolved in a short time, which also shortens the manufacturing time.

[0479] On the other hand, as in Patent Documents 3-5, if the sulfur-containing compound is not prepared into a solution beforehand and is mixed while remaining in powder form, the sulfur-containing compound will dissolve and remain. As a result, a large amount of foreign matter originating from the sulfur-containing compound is generated in the obtained photosensitive composition, leading to a large amount of foreign matter in the resist pattern formed using the photosensitive composition.

[0480] There are no particular limitations on the method of mixing the components; mixing and stirring using conventional methods is sufficient. Examples of devices that can be used to mix and stir the components include dissolvers, homogenizers, and three-roll mills. After the components are uniformly mixed, the resulting mixture can be further filtered using a sieve, membrane filter, or similar means.

[0481] If foreign matter originating from sulfur-containing compounds (C) is present in the unfiltered state, it is possible to reduce the content of sulfur-containing compounds (C) in the photosensitive composition by removing the foreign matter originating from sulfur-containing compounds (C). However, in this invention, since the sulfur-containing compounds (C) are dissolved in a specific solvent (S1), it is difficult to remove the sulfur-containing compounds (C) by filtration. Therefore, even when the photosensitive composition is filtered, it is difficult to reduce the content of sulfur-containing compounds (C), thereby obtaining the desired effect of sulfur-containing compounds (C).

[0482] Methods for manufacturing photosensitive dry films

[0483] The photosensitive dry film has a substrate film and a photosensitive layer formed on the surface of the substrate film, the photosensitive layer being composed of the aforementioned photosensitive composition.

[0484] As a substrate film, light transmittance is preferred. Specifically, examples include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film. From the viewpoint of achieving an excellent balance between light transmittance and tensile strength, polyethylene terephthalate (PET) film is preferred.

[0485] The photosensitive composition is coated onto a substrate film to form a photosensitive layer, thereby producing a photosensitive dry film.

[0486] When forming a photosensitive layer on a substrate film, a photosensitive composition is applied to the substrate film using a coater, bar coater, wire bar coater, roller coater, curtain coater, etc., and then dried, such that the film thickness after drying is preferably 0.5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less.

[0487] Photosensitive dry films may also have a protective film on the photosensitive layer. Examples of such protective films include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film.

[0488] Patterned resist film and manufacturing method of molded substrate

[0489] The method for forming a patterned resist film on a substrate using the photosensitive composition described above is not particularly limited. This patterned resist film is preferably used as an insulating film, an etching mask, or a mold for forming plated shapes.

[0490] A preferred method for manufacturing a patterned resist film includes the following steps:

[0491] The lamination process involves laminating a photosensitive layer composed of a photosensitive composition onto a substrate.

[0492] The exposure process involves selectively irradiating the photosensitive layer with active light or radiation.

[0493] The developing process involves developing the exposed photosensitive layer.

[0494] The manufacturing method of a molded substrate with a mold for forming a plated shape is the same as the manufacturing method of a patterned resist film, except that it includes a step of laminating a photosensitive layer on the metal surface of a substrate having a metal surface and using development in a development step to make a mold for forming a plated shape.

[0495] There are no particular limitations on the substrate used for stacking the photosensitive layer; conventionally known substrates can be used, such as substrates for electronic components or substrates on which a predetermined wiring pattern is formed. Silicon substrates or glass substrates can also be used as substrates.

[0496] When manufacturing a molded substrate with a mold for forming a plated shape, a substrate with a metallic surface is used as the substrate. Copper, gold, and aluminum are preferred as the type of metal constituting the metallic surface, with copper being more preferred.

[0497] When forming a resist pattern on a substrate with a metallic surface, defects such as irregular cross-sectional shapes, such as feet, are easily produced. However, since the above-mentioned photosensitive composition contains a sulfur-containing compound (C), the occurrence of such defects is suppressed, resulting in a resist pattern with the desired cross-sectional shape. Furthermore, since the amount of foreign matter originating from the sulfur-containing compound (C) in the above-mentioned photosensitive composition is reduced, a resist pattern with the desired shape can be formed. Moreover, since the sulfur-containing compound (C) is difficult to remove by filtration in the above-mentioned photosensitive composition, the desired effect of the sulfur-containing compound (C) can be obtained.

[0498] For example, a photosensitive layer can be laminated on a substrate in the following manner: a liquid photosensitive composition is coated on the substrate, and the solvent is removed by heating, thereby forming a photosensitive layer of the desired film thickness. The thickness of the photosensitive layer is not particularly limited as long as a resist pattern can be formed with the desired film thickness. The film thickness of the photosensitive layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, even more preferably 0.5 μm or more and 150 μm or less, and particularly preferably 0.5 μm or more and 200 μm or less.

[0499] The upper limit of the film thickness can be, for example, below 100 μm. The lower limit of the film thickness can be, for example, above 1 μm or above 3 μm.

[0500] Various methods can be employed for coating a photosensitive composition onto a substrate, including spin coating, slot coating, roller coating, screen printing, and applicator coating. Pre-baking of the photosensitive layer is preferred. The pre-baking conditions vary depending on the type and mixing ratio of the components in the photosensitive composition, the coating film thickness, etc., but are typically between 70°C and 200°C, preferably between 80°C and 150°C, for approximately 2 minutes to 120 minutes.

[0501] The photosensitive layer formed as described above is selectively irradiated (exposed) with active light or radiation, such as ultraviolet or visible light with wavelengths of 300 nm to 500 nm, through a mask with a prescribed pattern.

[0502] As radiation sources, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, and argon lasers can be used. In addition, radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, gamma rays, electron beams, proton beams, neutron beams, and ion beams. The radiation dose varies depending on the composition of the photosensitive composition and the thickness of the photosensitive layer; for example, when using an ultra-high-pressure mercury lamp, it is approximately 100 mJ / cm². 2 Above 10000mJ / cm 2Below. In addition, in order to produce acid, the radiation contains light that activates the acid-producing agent (A).

[0503] After exposure, the photosensitive layer is heated using known methods to promote the diffusion of acid, thereby changing the solubility of the photosensitive layer in the exposed portion of the photosensitive resin film to developing solutions such as alkaline developing solutions.

[0504] Next, the exposed photosensitive layer is developed using conventional methods to dissolve and remove unwanted portions, thereby forming a predetermined resist pattern or a mold for creating the plated object. An alkaline aqueous solution can be used as the developer at this stage.

[0505] As a developer, aqueous solutions of bases such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium methylsilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, and 1,5-diazabicyclo[4,3,0]-5-nonane can be used. Furthermore, aqueous solutions containing appropriate amounts of water-soluble organic solvents or surfactants such as methanol or ethanol can also be used as developers.

[0506] In addition, depending on the composition of the photosensitive composition, development using organic solvents can also be applied.

[0507] The development time varies depending on the composition of the photosensitive composition and the thickness of the photosensitive layer, and is usually between 1 minute and 30 minutes. The development method can be any of the following: liquid-based development, immersion development, water-pit development, or spray development.

[0508] After development, the substrate is rinsed with running water for 30 to 90 seconds and then dried using an air gun, oven, or similar method. In this way, a resist pattern patterned into a desired shape is formed on the metal surface of a substrate with a metal surface. Furthermore, it is possible to manufacture a substrate with a resist pattern on its metal surface in this manner.

[0509] Manufacturing Method of Plated Shaped Objects

[0510] In the non-resist portion (the portion removed by the developer) of the mold with a mold substrate formed using the above method, a conductor such as a metal is embedded by plating, thereby forming plated shapes such as bumps and metal pillars as connection terminals, or Cu redistribution. Furthermore, the plating process is not particularly limited, and various conventionally known methods can be used. As the plating solution, solder plating solution, copper plating solution, gold plating solution, and nickel plating solution are particularly preferred. The remaining mold is finally removed using a stripping solution or the like using conventional methods.

[0511] Example

[0512] The present invention will be described in more detail below through embodiments, but the present invention is not limited to these embodiments.

[0513] [Examples 1-29 and Comparative Examples 1-29]

[0514] In Examples 1-29 and Comparative Examples 1-29, compounds C1-C5 with the following formulas were used as sulfur-containing compounds (C).

[0515] [Chemistry 46]

[0516]

[0517] In Examples 1 to 29 and Comparative Examples 1 to 29, PAG-A1 to PAG-A4 of the following formulas were used as acid-producing agents (A).

[0518] [Chemistry 47]

[0519]

[0520] In Examples 1-29 and Comparative Examples 1-29, the following Resin-A1 to Resin-A5 were used as resins (Resin (B)) whose solubility in alkali increased due to the action of acid. The numbers in parentheses at the bottom right of each structural unit in the following structural formulas indicate the content (mass %) of each structural unit in the resin. Resin-A1 has a mass-average molecular weight Mw of 40,000 and a molecular weight distribution coefficient (Mw / Mn) of 2.6. Resin-A2 has a mass-average molecular weight Mw of 40,000 and a molecular weight distribution coefficient (Mw / Mn) of 2.6. Resin-A3 has a number-average molecular weight Mn of 98,000. Resin-A4 has a number-average molecular weight Mn of 98,000. Resin-A5 has a number-average molecular weight Mn of 98,000.

[0521] [Chemistry 48]

[0522] Resin-A1

[0523]

[0524] Resin-A2

[0525]

[0526] Resin-A3

[0527]

[0528] Resin-A4

[0529]

[0530] Resin-A5

[0531]

[0532] In Examples 1-29 and Comparative Examples 1-29, Resin-B1 (polyhydroxystyrene resin) and Resin-C (phenolic varnish resin (m-cresol condensate)) were used as alkali-soluble resins (D). The numbers in parentheses at the bottom right of each structural unit in the following structural formulas indicate the content (mass %) of each structural unit in the resin. Resin-B1 has a mass-average molecular weight (Mw) of 2500 and a molecular weight distribution coefficient (Mw / Mn) of 2.4. Resin-C has a mass-average molecular weight (Mw) of 8000.

[0533] [Chemistry 49]

[0534] Resin B1

[0535]

[0536] [Transformation 50]

[0537] Resin-C

[0538]

[0539] The following Amine-1 to Amine-3 were used as acid diffusion inhibitors (F).

[0540] Amine-1: ADK STAB LA-63P (manufactured by ADEKA)

[0541] Amine-2: Diphenylpyridine

[0542] Amine-3: Triphenylpyridine

[0543] (Examples 1-27)

[0544] Solutions (premixes) of γ-butyrolactone (GBL) containing the sulfur-containing compounds (C) listed in Tables 1 and 2 were obtained, with the sulfur-containing compound (C) being 1% by mass. The complete dissolution of the sulfur-containing compound (C) was visually confirmed.

[0545] In addition, the types and amounts of acid-producing agent (A), resin (B), alkali-soluble resin (D), and acid diffusion inhibitor (F) listed in Tables 1 and 2 were dissolved in 3-methoxybutylacetic acid (MA, δp: 4.1 MPa) with 0.05 parts by weight of surfactant (BYK310, manufactured by BYK Chemical Company) at a solid content concentration of 53% by weight. 0.5 After boiling point: 172℃, it is filtered using a membrane filter with a pore size of 1μm.

[0546] A γ-butyrolactone solution (premix) was added to the filtered solution to make the sulfur-containing compound (C) reach the values ​​recorded in Tables 1 and 2. The mixture was stirred for 30 minutes and allowed to stand for 4 hours to obtain the positive chemically amplified photosensitive compositions of Examples 1 to 27.

[0547] (Example 28)

[0548] Except for using dimethyl sulfoxide (DMSO) instead of γ-butyrolactone, the same procedure as in Example 1 was performed to obtain the positive chemically amplified photosensitive composition of Example 28.

[0549] (Example 29)

[0550] Except for using N-methyl-2-pyrrolidone (NMP) instead of γ-butyrolactone, the same procedure as in Example 1 was performed to obtain the positive chemically amplified photosensitive composition of Example 29.

[0551] (Comparative Examples 1-27)

[0552] The acid-producing agent (A), resin (B), alkali-soluble resin (D), and acid diffusion inhibitor (F) listed in Tables 3 and 4 were dissolved in 3-methoxybutylacetic acid (MA) with 0.05 parts by weight of surfactant (BYK310, manufactured by BYK Chemical Company) at a solid content concentration of 53% by weight. The solutions were then filtered through a membrane filter with a pore size of 1 μm.

[0553] Sulfur-containing compound (C) was added to the filtered solution in such a manner as the values ​​recorded in Tables 3 and 4, the mixture was stirred for 30 minutes and allowed to stand for 4 hours to obtain the positive chemically amplified photosensitive compositions of Comparative Examples 1 to 27.

[0554] (Comparative Example 28)

[0555] In addition to using methyl ethyl ketone (MEK, δp: 9.0 MPa) 0.5 (Boiling point: 80°C) In addition to γ-butyrolactone, the same operation as in Example 1 was performed to obtain the positive chemically amplified photosensitive composition of Comparative Example 28.

[0556] A methyl ethyl ketone solution (premix) in which sulfur compound (C) is dissolved at 1% by mass is a suspension in which sulfur compound (C) is insoluble. In addition, the resulting positive chemically amplified photosensitive composition is also a suspension.

[0557] (Comparative Example 29)

[0558] Except for using 3-methoxybutylacetic acid ester (MA) instead of γ-butyrolactone, the same operation as in Example 1 was performed to obtain the positive chemically amplified photosensitive composition of Comparative Example 29.

[0559] A 3-methoxybutylacetic acid solution (premix) in which sulfur compound (C) is dissolved at 1% by mass is a suspension in which sulfur compound (C) is insoluble. In addition, the resulting positive chemically amplified photosensitive composition is also a suspension.

[0560] The obtained positive chemically amplified photosensitive composition was evaluated according to the following method. The evaluation results are recorded in Tables 1 to 4.

[0561] [Evaluation of foreign objects]

[0562] A substrate with a sputtered copper layer on the surface of an 8-inch diameter silicon substrate was prepared. The positive chemical amplification photosensitive composition of the examples and comparative examples was coated onto the copper layer of this substrate to form a photosensitive layer (coating of the chemical amplification photosensitive composition) with a film thickness of 55 μm. Next, the photosensitive layer was pre-baked at 130°C for 5 minutes. After pre-baking, using a mask with a line and space pattern of 2.0 μm line width and 2.0 μm spacing, and a Canon PLA501F Hardcontact (manufactured by Canon Corporation), the pattern was exposed using ultraviolet light with a wavelength of 365 nm at an exposure dose 1.2 times the minimum exposure dose required to form a pattern of the specified size. Next, the substrate was placed on a heated plate and subjected to post-exposure heating (PEB) at 90°C for 1.5 minutes. Then, the following operation was repeated a total of 3 times: a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (TMAH) (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was added dropwise to the exposed photosensitive layer, and the mixture was left to stand at 23°C for 30 seconds. Afterward, the surface of the resist pattern was rinsed with running water and then purged with nitrogen gas to obtain the resist pattern.

[0563] The obtained resist pattern (wire spacing pattern) was randomly observed at 50 locations using an optical microscope (magnification: 10x) to confirm the presence or absence of foreign matter (dissolved residues of sulfur-containing compounds (C)). A rating of ◎ was given for 3 or fewer observed foreign matter, ○ for 4 to 9 observed foreign matter, × for 10 to 19 observed foreign matter, and ×× for 20 or more observed foreign matter. Furthermore, the size of the observed foreign matter was between 10 μm and 1 mm. Since filtration was performed before adding the sulfur-containing compound (C), the observed foreign matter can be considered to originate solely from the sulfur-containing compound (C).

[0564] [Table 1]

[0565]

[0566] [Table 2]

[0567]

[0568] [Table 3]

[0569]

[0570] [Table 4]

[0571]

[0572] As shown in Examples 1-29, the sulfur-containing compound (C), which is solid at room temperature, is pre-dissolved in the polarity term δp of the Hansen solubility parameter, which is 10 MPa. 0.5 The chemically amplified photosensitive composition obtained by mixing the solvent (S1) above with other components has fewer foreign matter in the formed resist pattern. Furthermore, the fact that there are fewer foreign matter in the formed resist pattern indicates that the chemically amplified photosensitive compositions of Examples 1 to 29 have fewer foreign matter.

[0573] On the other hand, according to Comparative Examples 1-29, the chemically amplified photosensitive compositions of Comparative Examples 1-27 obtained by adding a sulfur-containing compound (C) that is solid at room temperature while maintaining it in a powder (solid) state, or by pre-dissolving a sulfur-containing compound (C) that is solid at room temperature in a solution with a polarity term δp of the Hansen solubility parameter less than 10 (MPa) 0.5 The resist films formed by the chemically amplified photosensitive compositions of Comparative Examples 28 and 29, which were obtained by mixing the solvent with other components, contained more foreign matter.

Claims

1. A method for manufacturing a chemically magnified photosensitive composition, the chemically magnified photosensitive composition comprising an acid-generating agent (A) that generates acid upon irradiation by active light or radiation, a sulfur-containing compound (C) that is solid at room temperature, and a Hansen solubility parameter with a polarity term δp of 10 (MPa). 0.5 The solvent (S1) and the solvent (S2) different from the solvent (S1) are characterized in that, have: The process of preparing a sulfur-containing compound (C) solution by dissolving the sulfur-containing compound (C) in the solvent (S1); and The process of mixing the sulfur-containing compound (C) solution, the acid-generating agent (A), and the solvent (S2) The solvent (S1) is γ-butyrolactone, dimethyl sulfoxide, or N-methyl-2-pyrrolidone. The sulfur-containing compound (C) comprises at least one selected from compounds represented by formula (c1-1) and their tautomers, and compounds represented by formula (c2). [Chemistry 1] In equation (c1-1), Ring A is a monocyclic ring with 4 to 8 atoms. X 1c For -NR 13c -or =N-, R 13c The substituent is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms that may have substituents, an alkenyl group having 1 to 8 carbon atoms that may have substituents, an alkynyl group having 1 to 8 carbon atoms that may have substituents, or an aromatic group or carboxyl group having 4 to 20 carbon atoms that may have substituents. [Chemistry 2] In equation (c2), Y 1c and Y 2c Each is an independent nitrogen atom. R 21c and R 22c Each of the following can be independently composed of a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an alicyclic hydrocarbon group with 3 to 18 carbon atoms. R 23c The following groups are included: aliphatic hydrocarbon groups with 1 to 10 carbon atoms, aromatic hydrocarbon groups with 6 to 14 carbon atoms, alicyclic hydrocarbon groups with 3 to 18 carbon atoms, and -SR. 24c or -NR 25c R 26c , R 24c R 25c and R 26c R is independently a hydrogen atom, an aliphatic hydrocarbon group with 1 to 10 carbon atoms, an alicyclic hydrocarbon group with 3 to 10 carbon atoms, an aromatic hydrocarbon group with 6 to 14 carbon atoms, or an acyl group with 1 to 12 carbon atoms. 25c and R 26c The hydrogen atoms of aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and acyl groups can be replaced by hydroxyl groups. n and m are both 0.

2. The method for manufacturing the chemically amplified photosensitive composition as described in claim 1, characterized in that, The chemically amplified photosensitive composition is positive.

3. The method for manufacturing the chemically amplified photosensitive composition as described in claim 2, characterized in that, The chemically amplified photosensitive composition contains a resin (B) whose solubility in alkali increases due to the action of acid.

4. The method for manufacturing the chemically amplified photosensitive composition as described in claim 2, characterized in that, The chemically amplified photosensitive composition also contains an alkali-soluble resin (D).

5. The method for manufacturing the chemically amplified photosensitive composition as described in claim 4, characterized in that, The alkali-soluble resin (D) comprises at least one resin selected from the group consisting of phenolic varnish resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

6. A premixed solution for preparing a chemically amplified photosensitive composition obtained by the manufacturing method of claim 1, characterized in that, It contains sulfur-containing compounds (C) that contain sulfur atoms capable of coordinating with metals and are solid at room temperature.

7. A chemically amplified photosensitive composition obtained by the manufacturing method of claim 1, characterized in that, The content of the solvent (S1) relative to the total mass of the solvent (S1) and the solvent (S2) is greater than 0% by mass and less than 5% by mass.

8. The chemically amplified photosensitive composition as described in claim 7, characterized in that, The chemically amplified photosensitive composition is positive.

9. The chemically amplified photosensitive composition as described in claim 8, characterized in that, Resin (B) contains resins whose solubility in alkalis increases due to the action of acid.

10. The chemically amplified photosensitive composition as described in claim 8, characterized in that, It also contains alkali-soluble resin (D).

11. The chemically amplified photosensitive composition as described in claim 10, characterized in that, The alkali-soluble resin (D) comprises at least one resin selected from the group consisting of phenolic varnish resin (D1), polyhydroxystyrene resin (D2), and acrylic resin (D3).

12. A method for manufacturing a photosensitive dry film, characterized in that, include: A photosensitive layer is formed by coating a substrate film with the chemically amplified photosensitive composition according to any one of claims 7 to 11.

13. A method for manufacturing a patterned resist film, characterized in that, include: The lamination process involves laminating a photosensitive layer on a substrate, which is composed of the chemically amplified photosensitive composition according to any one of claims 7 to 11. The exposure process involves selectively irradiating the photosensitive layer with active light or radiation. The developing process involves developing the exposed photosensitive layer.

14. The method for manufacturing a patterned resist film as described in claim 13, characterized in that, The substrate is a substrate with a metal surface.

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